Salts of cationic-metal dry cave complexes

ABSTRACT

Salts containing cations of the formula:   &lt;IMAGE&gt;   (in which M is Co, Fe, Cr or Mn, X, Y, R1, R2 and R4 are hydrogen, alkyl or substituted groups, and the two R3 groups and/or the two R6 groups form an organic bridging group), and derivatives of these compounds having various axial ligands attached to the metal atom, complex oxygen reversibly and are thus useful for oxygen scavenging and separating oxygen from air. Other types of compounds having similar bridging groups are also useful for the same purpose.

The Government has rights in this invention pursuant to Contract NumberCHE-75-14837 awarded by the National Science Foundation.

This application is a continuation-in-part of my co-pending applicationSer. No. 114670 filed Jan. 23, 1980 and now abandoned.

BACKGROUND OF THE INVENTION

Oxygen is produced industrially in enormous quantities from air.Hitherto, substantially all industrially-produced oxygen has beenseparated from air by condensing the air and then fractionallydistilling the liquid air to separate the oxygen from nitrogen and othergases. This liquification procedure consumes very large amounts ofenergy, since the boiling point of oxygen at atmospheric pressure isonly 77° K.

The industrial demand for oxygen is growing and is expected to increasegreatly if and when large-scale production of synthetic fuels begins,since most of the processes for liquification of coal and similarmethods of producing synthetic fuels require large quantities of oxygen.In view of the known disadvantages of the air liquification process,attention has recently been directed toward methods for the separationof oxygen from air at temperatures much closer to ambient. In principle,such separation methods are very simple; a solution is preparedcontaining a compound which can complex molecular oxygen in a mannersimilar to that of the known biological oxygen-containing proteins,myoglobin and hemoglobin, this solution is exposed to air or a similaroxygen-containing gas so that a large proportion of theoxygen-containing compound becomes complexed with oxygen, then thesolution is removed from contact with the air and exposed to anenvironment in which the oxygen partial pressure is less than that inequilibrium with the oxygen-complexed compound, so that theoxygen-complexed compound gives up at least part of its oxygen, therebyreleasing into the environment a gas much richer in oxygen than the airwith which the solution was originally in contact (a small amount ofnitrogen and other gases almost invariably comes over with the oxygenbecause of the solubility of the other gases in the solution). Iffurther purification is desired, the process can be repeated to yield agas even richer in oxygen.

Perhaps the most promising techniques for thus separating oxygen fromair involve the use of so-called "immobilized liquid membranes". Suchimmobilized liquid membranes comprise a solid support, typically asynthetic polymer, which is inert to oxygen, together with liquidimmobilized on the inert support. The support may have very fine holestherein so that the liquid cannot run through the porous material, apolymer film acting as the support may be swollen by contact with theliquid, or various other techniques may be used for immobilizing theliquid on the support. Air or some other oxygen-containing gas is passedover one side of the immobilized liquid membrane, while the gas whichpasses through the membrane is removed by pumping on the opposite sideof the membrane. The oxygen "diffuses selectively" through the liquidmembrane; in fact, since there is an oxygen partial pressure gradientbetween the two sides of the membrane, the oxygen molecules are carriedin the form of a metal complex through the immobilized liquid membraneat a much greater rate than the rate at which other gases pass throughthe membrane. More detailed descriptions of such immobilized liquidmembrane gas separation techniques are given in U.S. Pat. No. 3,396,510issued August 13, 1968 to Ward et al; Chemical Engineering, July 13,1981, page 63; Parrett Membranes Succeeding by Separating, Technology,March/April 1982, page 16; Scholander, Science, 131, 585 (1960), Bassettet al, Non-Equilibrium Facilitated Diffusion of Oxygen Through Membranesof Aqueous Cobaltodihistidine, Biochim. Biophys. Acta., 211, 194 (1970);Science News, March 6, 1982, page 151; and a Technical Brief, OxygenEnrichment, published by Bend Research, Inc., 64550 Research Road, Bend,Oregon 97701 (Autumn 1981): the disclosures of all these documents areherein incorporated by reference.

Heretofore, synthetic oxygen carriers have proven unsuccessful inaqueous solutions. For instance, the many well-known 1:1 dioxygenadducts of cobalt(II) suffer from at least one of four major limitationswhen compared to the coboglobins: they exist only at low temperature,they do not exist in aqueous solutions, they rapidly react further toform the 2:1 μ-peroxo complexes, and they do not approach coboglobin instability (as measured by the equilibrium constant Keq). A goodunderstanding of this area can be gained by reading Jones et al,Synthetic Oxygen Carriers Related to Biological Systems, ChemicalReviews, 79(2), 139-179 (1979).

The present invention relates to salts of metal dry cave complexesuseful for complexing molecular oxygen. For present purposes, a "drycave" is a cavity in the vicinity of a vacant metal coordination site ofthe complex which can reversibly accommodate molecules. Such cavity canbe made hydrophobic by providing interior walls consisting almostentirely of filled π-orbitals. Thus, the metal dry cave complexes canreversibly bind small molecules such as dioxygen even in aqueoussolutions. As such, the metal dry cave complexes can effectively emulatevarious protein complexes such as, for example, myoglobin, hemoglobin,and the like.

Heretofore, nickel dry cave complexes have been proposed (Schammel,Thesis, The Ohio State University, Columbus, Ohio, 1976; Busch et al,Control of Potentials of Metal Ion Couples in Complexes of MacrocyclicLigands by Ligand Structural Modifications, Reprint of ACS SymposiumSeries, No. 38. Electrochemical Studies of Biological Systems, AmericanChemical Society, 1977). Cobalt and iron derivatives were attempted, butit is now known that such attempts were fruitless.

SUMMARY OF THE INVENTION

(Since the formulae shown in the accompanying drawings are formulaeshowing only the cation of a salt, references hereinafter to a compoundor salt of Formula--are to a compound or salt containing a cation of thespecified formula.)

In one aspect this invention provides a salt of a cationic metal complexof Formula XVII in FIG. 1 of the accompanying drawings wherein:

M is Co, Fe, Cu or Mn;

n⁺ is a positive oxidation state of M, n being not greater than 3;

X and Y are each independently an o-phenylene, ethylene, trimethylene,2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or2-(N-methyl-2-pyridino)-trimethylene group;

each R₁ independently is hydrogen or a methyl group;

each R₂ independently is hydrogen or a methyl group;

each R₃ independently is hydrogen, an alkyl group containing not morethan about 17 carbon atoms, a benzyl group, a phenyl group, or a phenylgroup substituted by a halogen atom or by one or two methoxy groups; orthe two R₃ groups together form a carbon-carbon bridge, saidcarbon-carbon bridge comprising a polymethylene bridge containing from 7to about 12 carbon atoms or an m- or p-xylylene group;

each R₄ independently is hydrogen, an alkyl group containing not morethan about 4 carbon atoms, a cyanoalkyl group containing not more thanabout 4 carbon atoms, a phenyl group or a benzyl group;

each R₆ independently is hydrogen or a methyl group; or the two R₆groups together form a nitrogen-nitrogen bridge, said nitrogen-nitrogenbridge comprising a polymethylene group containing from 4 to about 12carbon atoms, a polymethylene group containing from 4 to about 12 carbonatoms and substituted by a methoxycarbonyl group, or a grouping of theformula:

    --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --

where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylenegroup, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group,a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylenegroup, a sulfur atom, an imino group, or a methylimino group, subject tothe proviso that when G is a sulfur atom, an imino group or amethylimino group, the sum of a and b is at least 4;

or the two NR₄ R₆ groups together form a bis-piperazino bridge of theformula ##STR2## where D is a 1,3-phenylene group, a 1,4-phenylenegroup, a 1,4-phenylene group substituted by one or more methyl groups, a9,10-anthracene group or a 2,6-pyridylene group,

subject to the proviso that when the two R₃ groups do not form acarbon-carbon bridge, either the two R₆ groups must form anitrogen-nitrogen bridge or the two NR₄ R₆ groups must form abis-piperazino bridge.

In another aspect, this invention provides a salt comprising a cationicmetal complex of Formula XVIIA in FIG. 1 of the accompanying drawings,wherein M,n⁺, X, R₁, R₂, R₃, R₄ and R₆ have the same definitions as inFormula XVII and Z is an electron donor selected from the groupconsisting of the halide ions, cyanate, thiocyanate, azide,acetonitrile, water, an alkanol containing not more than about fivecarbon atoms, pyridine, 4-aminopyridine, imidazole andN-methylimidazole.

The invention extends to an adduct of the salts of Formulae XVII andXVIIA in FIG. 1 of the accompanying drawings and molecular oxygen orcarbon monoxide.

In a further aspect, the invention provides a salt of Formula III inFIG. 1 of the accompanying drawings wherein:

    M.sup.n+ is Ni.sup.2+ ;

X and Y are each independently an o-phenylene, ethylene, trimethylene,2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or2-(N-methyl-2-pyridino)-trimethylene group;

each R₁ independently is hydrogen or a methyl group;

each R₂ independently is hydrogen or a methyl group;

each R₄ independently is hydrogen, an alkyl group containing not morethan about 4 carbon atoms or benzyl;

each R₆ independently is hydrogen or a methyl group; and

R₅ is a polymethylene group containing from 7 to about 12 carbon atomsor a m- or p-xylylene group.

In yet a further aspect, the invention provides a salt of Formula II inFIG. 1 of the accompanying drawings wherein:

M^(n+) is Ni²⁺ ;

X and Y are each independently an o-phenylene, ethylene, trimethylene,2-(2-pyridyl)-trimethylene; 2-methyl substituted trimethylene or2-(N-methyl-2-pyridino)-trimethylene group;

each R₁ independently is hydrogen or a methyl group;

each R₂ independently is hydrogen or a methyl group;

each R₄ independently is hydrogen or a methyl group;

R is a polymethylene group containing from 4 to about 12 carbon atoms, apolymethylene group containing from 4 to about 12 carbon atoms andsubstituted by a methyoxycarbonyl group, or a grouping of the formula--(CH₂)_(a) --G--(CH₂)_(b) -- where a and b are each independently 1, 2or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, amethoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, animino group or a methylimino group, subject to the proviso that when Gis a sulfur atom, an imino group or a methylimino group, the sum of aand b is at least 4; and

R₅ is a polymethylene group containing from 7 to about 12 carbon atomsor an m- or p-xylylene group.

In yet a further aspect, the invention provides a salt of Formula XVIIIin FIG. 1 of the accompanying drawings wherein:

M^(n+) is Ni²⁺ ;

X and Y are each independently an o-phenylene, ethylene, trimethylene,2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or2-(N-methyl-2-pyridino)-trimethylene group;

each R₁ independently is hydrogen or a methyl group;

each R₂ independently is hydrogen or a methyl group;

each R₃ independently is hydrogen, a methyl group or a phenyl group; and

D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene groupsubstituted by one or more methyl groups, a 9,10-anthracene group or a2,6-pyridylene group.

In yet a further aspect the invention provides a method for removingmolecular oxygen from a gaseous mixture, which comprises exposing a saltof Formula XVII or XVIIA in FIG. 1 to the gaseous mixture therebyallowing the cationic metal complex of the salt to complex molecularoxygen and thus to absorb oxygen from the gaseous mixture.

The invention also provides a method for increasing the proportion ofmolecular oxygen in a gaseous mixture, which comprises:

passing the gaseous mixture over one face of an immobilized liquidmembrane containing an oxygen-containing compound of Formula XVII orXVIIA in FIG. 1 of the accompanying drawings;

allowing molecular oxygen to diffuse selectively through saidimmobilized liquid membrane;

removing from adjacent the opposed face of the immobilized liquidmembrane an oxygen-enriched gas containing a higher proportion ofmolecular oxygen than the original gaseous mixture.

The invention also provides an oxygen-binding polymer comprising apolymeric support having attached thereto bridging groups or moleculesof the Formula XIX, XIX A or XIXB shown in FIG. 6 of the accompanyingdrawings wherein:

M is Co, Fe, Cu or Mn;

n⁺ is a positive oxidation state of M, n being not greater than 3;

X and Y are each independently an o-phenylene, ethylene, trimethylene,2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or2-(N-methyl-2-pyridino)-trimethylene group;

each R₁ independently is hydrogen or a methyl group;

each R₂ independently is hydrogen or a methyl group;

each R'₃ independently is hydrogen, an alkyl group containing not morethan about 17 carbon atoms, a benzyl group, a phenyl group, or a phenylgroup substituted by a halogen atom or by one or two methoxy groups;

each R₄ independently is hydrogen, an alkyl group containing not morethan about 4 carbon atoms, a cyanoalkyl group containing not more thanabout four carbon atoms, a phenyl group or a benzyl group;

each R'₆ independently is hydrogen or a methyl group; and

Z is an electron donor selected from the group consisting of the halideions, cyanate, thiocyanate, azide, acetonitrile, water, an alkanolcontaining not more than about five carbon atoms, pyridine,4-aminopyridine, imidazole and N-methylimidzole. In the case of themolecules of Formula XIX B, the polymer must be provided withelectron-donating groups which can coordinate with the metal ion M^(n+),thereby securing the molecule of Formula XIX B to the polymer. Ineffect, the electron-donating group and attached polymer function asdoes the ligand Z in other compounds of the invention.

The invention also provides a compound of Formula XX shown in FIG. 7 ofthe accompanying drawings wherein R₇ is a polymethylene group containingfrom 7 to about 16 carbon atoms or a group of the formula: ##STR3##where c+d equals an integer of from 4 to about 12; and R₈ is apolymethylene chain containing from 1 to about 10 carbon atoms,

or a complex of such a compound with a nickel, cobalt, iron, copper ormanganese ion in a +2 or +3 oxidation stage, this ion being co-ordinatedby the two nitrogen atoms and the two oxygen atoms of the compound anddisplacing the two hydroxyl protons thereof.

The invention also provides a compound of the Formula XXI shown in FIG.7 of the accompanying drawings wherein M is cobalt, iron, copper ormanganese, n⁺ is a positive oxidation state of M, n being not greaterthan 3, and R₉ is a bridging group of the formula

    --Q--(CH.sub.2).sub.e --Q--

wherein each Q independently is a methylene group, an imine group or anoxygen or sulfur atom and and e is from 5 to about 10,

or a bridging group of the formula

    --Q--(CH.sub.2).sub.f --(C.sub.6 H.sub.4)--(CH.sub.2).sub.g --Q--

wherein Q is as defined above, f+g equals from 3 to about 9 and C₆ H₄represents a phenylene group, M is nickel, cobalt, iron, copper ormanganese and n⁺ is a positive oxidation state of M, n being not greaterthan 3.

The invention also provides a compound of one of the FormulaeXXIIA-XXIIE shown in FIG. 7 of the accompanying drawings wherein

q is 2 or 3; and

R₁₀ is a bridging group of the formula

    --Q--(CH.sub.2).sub.r --Q--

where each Q independently is a methylene group, an imine group or anoxygen or sulfur atom and r is from 4 to about 10

or a bridging group of the formula

    --Q--(CH.sub.2).sub.h --(C.sub.6 H.sub.4)--(CH.sub.2).sub.i --Q--

where Q is as defined above, h+i equals from 2 to about 7 and C₆ H₄represents a phenylene group,

or a complex of such a compound with a nickel, cobalt, iron, copper ormanganese ion in a +2 or +3 oxidation state, this ion being coordinatedby the four central nitrogen atoms.

The invention also provides a compound of Formula XXIII in FIG. 7 of theaccompanying drawings wherein,

R₁₁ is hydrogen or an alkyl group; and R₉ is as defined above withreference to Formula XXI,

or a complex of such a compound wherein a single nickel, cobalt, iron,copper or manganese ion in a +2 or +3 oxidation state is coordinatedwith all four nitrogen atoms.

The invention also provides a compound of Formula XXIV in FIG. 7 of theaccompanying drawings wherein R₁₀ is as defined above with reference toFormula XXII; and R₁₂ is hydrogen or an alkyl group.

The invention also provides a compound of the Formula XXV in FIG. 7 ofthe accompanying drawings wherein:

m is 2 or 3;

R₁₃ is hydrogen or an alkyl group; and

R₁₅ is a polymethylene group containing at least about 8 carbon atoms, agrouping of one of the formulae:

    --(C.sub.6 H.sub.4)--O--(CH.sub.2).sub.v --O--(C.sub.6 H.sub.4)--,--(C.sub.6 H.sub.4)--O--(CH.sub.2).sub.j --(C.sub.6 H.sub.4)--(CH.sub.2).sub.k --O--(C.sub.6 H.sub.4)--,

(1,7-naphthylene)--O--(CH₂)_(v) --O--(1,7-naphthylene)- and-(1,7-naphthylene)--O--(CH₂)_(j) --(C₆ H₄)--(CH₂)_(k)--O--(1,7-naphthylene)-where (C₆ H₄) represents a phenylene group (whichmay be the ortho, meta or para-isomer) group, v is an integer from about4 to about 10 and, and j and k are two integers whose sum is from about4 to about 10;

or a complex of such a compound wherein the two protons of the centralimine groups are replaced by a single nickel, cobalt, ion, copper ormanganese ion in a +2 or +3 oxidation state, this ion also beingco-ordinated with the remaining three nitrogen atoms.

Finally, the invention also provides a process for complexing oxygenusing a compound of Formula XXVI in FIG. 7 of the accompanying drawingswherein M, n⁺ and R₉ are as defined above with reference to Formula XXI.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows Formulae XVII and XVIIA, together with the further FormulaeI, IA, II, IIA, III, IIIA, XVIII and XVIIIA which represent sub-groupsof compounds falling within Formulae XVII and XVIIA;

FIG. 2 shows Formula IV, a schematic stereochemical representation ofone compound of the invention;

FIG. 3 shows various synthetic methods used to prepare compounds of theinvention, together with the structure of the compound produced inExample VII below;

FIG. 4 shows a simple apparatus which can be used to separate oxygenfrom air using the compounds of the invention.

FIG. 5 shows the formula of a dimeric complex which may be produced asan impurity during the preparation of a compound of Formula I;

FIG. 6 shows the Formulae XIX and XIX A of the radicals used in theoxygen-binding polymers of the invention;

FIG. 7 shows Formulae XX-XXVI of the compounds of the invention which donot fall within Formulae XVII or XVII A, together with the methods usedfor synthesizing these compounds; and

FIG. 8 is a reaction scheme showing the synthesis used in Examples201-212 below.

DETAILED DESCRIPTION OF THE INVENTION Compounds of Formulae I-XVIII andI A-XVIII A

It will be observed that the compounds of Formula XVIIA differ from theclosely-related compounds of Formula XVII only by the presence of afifth ligand coordinated to the metal atom. This fifth ligand is anelectron donor which serves to donate electrons to the metal atom.

In the instant compounds of Formula XVII, the preferred anions arehexafluorophosphate, tetrachlorozincate, perchlorate,hexafluoroarsenate, fluoroborate, trifluoromethylsulfonate and thehalides, hexafluorophosphate and chloride anions being especiallypreferred. The preferred metal ions M^(n+) are Co²⁺, Co³⁺, Fe²⁺, Fe³⁺,Cu²⁺, Mn²⁺ and Mn³⁺, the Co²⁺ and Fe²⁺ ions being especially preferred.The group R₁ is preferably hydrogen, while the group R₂ is preferablymethyl. When two separate groups R₃ are present, each group ispreferably hydrogen, a methyl group, a phenyl group, a t-butyl group, ann-heptyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, a4-fluorophenyl group or a 3,5-dimethoxyphenyl group; when the two R₃groups together form a carbon-carbon bridge, this bridge is preferably apolymethylene group containing 7 to 10 carbon atoms or a m-xylylenegroup.

The preferred R₄ groups in Formula XVII are hydrogen, a methyl group, ann-propyl or n-butyl group, a 2-cyanoethyl group or a benzyl group.

When the two R₆ groups in Formula XVII together form a nitrogen-nitrogenbridge, this bridge preferably comprises a polymethylene bridge of 4 toabout 12 carbon atoms, an m- or p-xylylene group, a(5-methoxy)-m-xylylene group, a --(CH₂)₃ --(9,9-flourylene)--(CH₂)₃ --group, a --(CH₂)₄ CH(COOCH₃)(CH₂)₄ -- group, a --CH₂--(1,3-cyclohexylene)--CH₂ -- group, a --(CH₂)₂ C(CH₃)₂ (CH)₂ -- group,a 3-thiapentamethylene group, a 3-thiahexamethylene group, a --CH₂--(5-methoxycarbonyl-1,3-phenylene)--CH₂ --group, a 2,6-pyridylenegroup, a 4-azaheptamethylene group, or a 4-aza-4-methylheptamethylenegroup.

In Formula XVII, X is preferably an ethylene, trimethylene,2-(2-pyridyl)trimethylene group or a2-(N-methyl-2-pyridino)-trimethylene group, while Y is preferably atrimethylene group. The preferred anions are hexafluorophosphate andchloride.

The preferred substituents in Formula XVIIA are the same as those inFormula XVII.

It is believed that, for certain purposes, such as producing oxidationcatalysts, it is advantageous to immobilize the compounds of FormulaeXVII and XVIIA by grafting or otherwise chemically bonding the compoundsto oligomer or polymer chains. This grafting or chemical bonding of thecompounds of Formula XVII and XVIIA is conveniently accomplished byusing a compound in which at least one of the groups R₄ is hydrogen andbonding the compound of Formula XVII or XVIIA to the oligomer or polymerat this point. Alternatively, one may employ polymers having pendantgroups (e.g. pyridyl) which can function as a ligand Z, and use acompound of Formula XVII, thereby attaching the compound of Formula XVIIto the polymer by permitting one of the pendant groups on the polymer tofunction as a ligand Z in the compound of Formula XVIIA.

The preferred compounds of Formula XVII can conveniently be divided intofour groups as follows:

(a) The compounds in which two separate R₃ groups are present, but thetwo R₆ groups together form a carbon-carbon bridge. These are thecompounds of Formula I in FIG. 1 of the accompanying drawings, in whichM, n³⁰ , R₁, R₂, R₃, R₄, X and Y are as defined above with reference toFormula XVII and R is a polymethylene group containing from 4 to about12 carbon atoms, a polymethylene group containing from about 4 to about12 carbon atoms and substituted by a methoxycarbonyl group, or agrouping of the formula:

    --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --

where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylenegroup, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group,a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylenegroup, a sulfur atom, an imino group, or a methylimino group, subject tothe proviso that when G is a sulfur atom, a imino group or a methyliminogroup, the sum of a and b is at least 4.

(b) The compounds in which the two R₃ groups together form acarbon-carbon bridge, while two separate R₆ groups are present. Theseare the compounds of Formula III in FIG. 1 of the accompanying drawings,in which M, n⁺, R₁, R₂, R₄, X and Y are as defined above with referenceto Formula XVII, each R₆ group independently is hydrogen or a methylgroup and R₅ is a polymethylene group containing from about 7 to about12 carbon atoms or a m- or p-xylylene group.

(c) The compounds in which the two R₃ groups together from acarbon-carbon bridge, and the two R₆ together form a nitrogen-nitrogenbridge. These are the compounds of Formula II in FIG. 1 of theaccompanying drawings, wherein M, N⁺, R₁, R₂, R₄, X and Y are as definedabove with reference to Formula XVII; R is a polymethylene groupcontaining from 4 to about 12 carbon atoms, a polymethylene groupcontaining from about 4 to about 12 carbon atoms and substituted by amethoxycarbonyl group, or a grouping of the formula:

    --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --

where a and b are each independently 1,2 or 3 and G is a 1,3-phenylenegroup, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group,a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylenegroup, a sulfur atom, an imino group, or a methylimino group, subject tothe proviso that when G is a sulfur atom, a imino group or a methyliminogroup, the sum of a and b is at least 4; and R₅ is a polymethylene groupcontaining from 7 to about 12 carbon atoms or a m or p-xylylene group.

(d) The compounds in which the two NR₄ R₆ groups together form abispiperazino bridge. These are the compounds of Formula XVIII in FIG. 1of the accompanying drawings, wherein M, n⁺, R₁, R₂, R₃, X and Y are asdefined above with reference to Formula XVII, the two NR₄ R₆ groupstogether form a bispiperazino bridge and D is a 1,3-phenylene group, a1,4-phenylene group, a 1,4-phenylene group substituted by one or moremethyl groups, a 9,10-anthracene group or a 2,6-pyridylene group.

Formulae IA, IIIA, IIA, and XVIIIA in FIG. 1 of the accompanyingdrawings represent four sub-sets of compounds falling within FormulaXVIIA; the definitions of the various substituents in Formulae IA, IIA,IIIA, and XVIIIA are exactly the same as those of the same substituentsin Formulae I, II, III and XVIII respectively, while in each of theFormulae IA, IIA, IIIA and XVIIIA the ligand Z has the same meaning asdefined above with reference to Formula XVIIA.

In the compounds of Formula I, the preferred metal ions and groups R₁,R₂, R₄, R₆ and the anion are the same as those in the compounds ofFormula XVII, while the group R is preferably a polymethylene bridge of4 to about 8 carbon atoms, an m- or p-xylylene group, a(5-methoxy)-m-xylylene group, a --(CH₂)₃ --(9,9-flourylene)--(CH₂)₃ --group, a --(CH₂)₄ CH(COOCH₃)(CH₂)₄ -- group, a --CH₂--(1,3-cyclohexylene)--CH₂ -- group, a --(CH₂)₂ C(CH₃)₂ (CH₂)₂ -- group,a 3-thiapentamethylene group, a 3-thiahexamethylene group, a --CH₂--(5-methyoxycarbonyl-1,3-phenylene)--CH₂ --group, a 2,6-pyridylenegroup, a 4-azaheptamethylene group, or a 4-aza-4-methylheptamethylenegroup. An especially preferred group of compounds of Formula I are thosein which M^(n+) is Co²⁺, Co³⁺, Fe.sup. 2+, Fe³⁺, Mn²⁺, Mn³⁺ or Cu²⁺,each R₁ is hydrogen, each R₂ is a methyl group, each R₃ is hydrogen, amethyl group, a t-butyl group, and n-heptyl group, a 4-methoxyphenylgroup, a 4-chlorophenyl group, a 4-fluorophenyl group or a3,5-dimethoxyphenyl group, R₄ is hydrogen or a methyl group, R is apolymethylene group containing 4 to 8 carbon atoms, a m or p-xylylenegroup and the anion is hexafluorophosphate or chloride.

In the compounds of Formula III, the preferred metal ions are Co²⁺ andFe²⁺, X and Y are preferably each a dimethylene or trimethylene group,while R₁ is preferably hydrogen. The preferred R₄ groups are hydrogen,methyl, n-propyl and benzyl, while R₅ is preferably a polymethylenegroup containing from 7 to 9 carbon atoms and the anions is preferablyhexafluorophosphate or chloride. An especially preferred sub-group ofcompounds of Formula III is that in which each of the substituents havethe preferred values given above. In the salts of Formula II, X and Yare preferably each a trimethylene group, each R₁ group is preferablyhydrogen, each R₂ is preferably a methyl group, each R₄ is preferablyhydrogen, R₅ is preferably a polymethylene group containing from 7 to 10carbon atoms and R is preferably a polymethylene group containing 6 or 7carbon atoms or an m-xylylene group. The preferred anion ishexafluorophosphate. Again, a specifically preferred sub-group of saltsof Formula II is that in which each of the substituents has thepreferred value given above.

In the salts of Formula XVIII, the preferred metal ions are Co²⁺, Fe²⁺or Cu²⁺, while X is preferably a trimethylene group or a2-(N-methyl-2-pyridino)trimethylene group and Y is preferably atrimethylene group. Also in the salts of Formula XVIII, R₁ is preferablyhydrogen, R₂ is preferably methyl and R₃ is preferably methyl or phenyl.The preferred groups D are 1,3-phenylene, 1,4-phenylene,tetramethyl-1,4-phenylene, 9,10-anthracene and 2,6-pyridylene. Thepreferred anions of hexafluorophosphate and chloride. Again, anespecially preferred sub-group of salts of Formula XVIII is that inwhich each of the substituents has the preferred values given above.

Specific preferred compounds of Forumula I are:

[(2,3,8,9,11,17-hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;

[(2,3,9,10,12,18-hexamethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;

[(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;

[(3,8,11,17-tetramethyl-2,9-diphenyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;

[(3,9,12,18-tetramethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;

[(3,10,13,19-tetramethyl-2,11-diphenyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;

[(2,10,12,18-tetramethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;

[(2,11,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;

[(2,7,12,14,20-pentamethyl-3,7,11,15,19,22,26-heptaazabicyclo[11.7.7]heptacosa-1,12,14,19,21,26-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;

[(12,18-dimethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;

[(13,19-dimethyl-2,11-diphenyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate; and

[(2,3,10,11,13,19-hexamethyl-23-(2-pyridyl)-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.

A specific preferred compound of Formula III is:

[(12,18-dimethyl-2,10-bis-methylamino-13,17,20,24-tetraazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate

A specific preferred compound of Formula XVIII is:

[(2,9,10,17,19,25,33,34-octamethyl-3,6,13,16,20,24,27,31-octaazapentacyclo[16.7.7.2⁸,11.2³,6.2¹³,16]octatriaconta-1,8,10,17,19,24,26,31,33-nonaene-κ⁴ N)cobalt(II)]hexafluorophosphate.

In Formula IA, each R₁ is preferably hydrogen and each R₂ is preferablymethyl. Each R₃ is preferably is hydrogen, a methyl group, a phenylgroup, a t-butyl group, an n-heptyl group, a 4-methoxyphenyl group, a4-chlorophenyl group, a 4-fluorophenyl group or a 3,5-dimethoxyphenylgroup, while each R₄ is preferably hydrogen, a methyl group or a benzylgroup. R is preferably a polymethylene bridge of 4 to about 12 carbonatoms, an m- or p-xylylene group or a --(CH₂)₃--(9,9-flourylene)--(CH₂)₃ -- group, and X and Y are preferably each atrimethylene group. The preferred ligands Z are chloride, cyanate,thiocyanate, azide, ethanol, acetonitrile, pyridine, 4-aminopyridine,imidazole or N-methylimidazole. The preferred anions arehexafluorophosphate and chloride. Again, a specifically preferredsub-group of compounds of Formula IA are those wherein each of thesubstituents has one of the preferred values given above.

The preferred sub-group of compounds of Formula IIIA are those in whichthe metal is cobalt or iron, n is 2, each R₁ is hydrogen, each R₂ and R₄is hydrogen or a methyl group, each R₃ is hydrogen, a methyl group, anethyl group, a n-propyl group or a benzyl group, X and Y are each atrimethylene group, R₅ is a polymethylene group containing 7 to 10carbon atoms, Z is chloride, acetonitrile or water and the anion ishexafluorophosphate.

In the source of Formula XVIIIA, the metal ion is preferably Co²⁺ orFe²⁺, X and Y are preferably each a trimethylene group and each R₁ ispreferably hydrogen. Each R₂ and R₃ is preferably a methyl group, whileD is preferably a 1,3-phenylene group, a 1,4-phenylene group, atetramethyl-1,4-phenylene group or a 9,10-anthracine group. Thepreferred anion is hexafluorophosphate. Again, a preferred sub-group ofcompounds are of Formula XVIIIA of those in which each of thesubstituents has the preferred values given above.

Specific preferred salts of Formula IA are:

[chloro(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;

[chloro(2,12-di-n-heptyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;

[chloro(2,12-di-p-methoxyphenyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;

[chloro(2,12-di-p-chlorophenyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluoro-phosphate;

[chloro(2,12-di-p-fluorophenyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;

[acetonitrile(14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)cobalt(II)]hexafluorophosphate;

[acetonitrile(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;

[acetonitrile(3,11-dibenzyl-2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;

[acetonitrile(3,11,14,20-tetramethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;

[acetonitrile(3,11-dibenzyl-14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;

[acetonitrile(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazabicyclo[11.7.7]heptacosa-1,12,14,19,21,26-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;

[acetonitrile(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)cobalt(II)]hexafluorophosphate; and

[acetonitrile(3,10,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.

Specific preferred salts of Formula IIIA are:

[chloro(2,10-bis-dimethylamino-12,18-dimethyl-13,17,20,24-tetraazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)iron(II)] hexafluorophosphate;

[chloro(2,11-bis-dimethylamino-13,19-dimethyl-14,18,21,25-tetraazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)iron(II)] hexafluorophosphate;

[acetonitrile(12,18-dimethyl-2,10-bis-propylamino-13,17,20,24-tetraazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate; and

[acetonitrile(2,11-bis-dimethylamino-13,19-dimethyl-14,18,21,25-tetraazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.

It should be noted that certain of the possible anions (e.g. chloride)in the salts of Formula XVII A can also function as the ligand Z in thesame salts. Thus, as those skilled in the art will appreciate, whenpreparing for example a salt of Formula XVII A in which the anion ischloride but Z is not chloride, some replacement of the ligand Z withchloride may occur and it may be difficult to prepare the desired saltin a pure form, especially when the metal M is iron.

A somewhat similar problem exists with respect to the metal atom M. Asdescribed below, the salts of Formulae XVII and XVII A may besynthesized via a tetrachlorozincate salt of the corresponding nickelcation. However, if one attempts to prepare a salt of Formula XVII orXVII A having M=Co, the cobalt and zinc compete for the metalcoordination site in the cation and it is often not possible to preparepure cobalt salts in the presence of tetrachlorozincate anion. It is forthis reason that it is preferred to convert the tetrachlorzincate saltto the corresponding hexafluorophosphate salt during the synthesis, asdescribed below.

A most striking feature of the dry cave cation complexes in the salts ofFormulae XVII and XVIIA is the configuration and conformation of themacrocycle and the bridge(s) which form(s) the interior walls and roofof the dry cave site. FIG. 2 of the accompanying drawings shows thestereochemistry of a compound of Formula I A, this being the cation ofFormula I where in M^(n+) =Fe²⁺, R₁ =H, R₂ =CH₃, and X=Y trimethylene.The bridge R (and all other R₅ or bis-piperazino bridges) effectivelyforms both the roof and back of the cave by its tilt, yet itsdisplacement from over the center of the metal ion leaves a wide openingor mouth to the cave, the base of which is formed by the square planararrangement of nitrogen atoms around the metal ion. Thus, smallmolecules, such as dioxygen and carbon monoxide, for example, can beaccommodated in the dry cave and protected from the surroundingenvironment, especially when an axial ligand Z is coordinated to themetal from the side opposite the bridging group (the ligand Z isdisposed directly below the metal ion M in Formula IV). The metal drycave cation complexes, then, can combine with molecular oxygen (dioxygenor O₂) or promote reactions of the dioxygen molecule, or promotereactions of its derived intermediate reaction products including O₂ ⁻,HO₂, O₂ ²⁻, H₂ O₂, etc. The oxygen adducts of the cation complexes canand do exist efficaciously in solution in various solvents, includingwater. Further, certain of the oxygen-adducts have shown remarkablethermal stability not only at room temperature but also at temperaturesranging upwards to 40°-50° C. Such thermal stability is quiteunexpected, though certainly a propitious property possessed by thesalts of the present invention.

All the utilities of the salts of Formulae XVII and XVIIA suggestedherein are based upon the ability of the cation complexes of the saltsto complex with oxygen and other small molecules such as carbonmonoxide. Firstly, the salts of Formula XVII and XVIIA are useful forscavenging low levels of molecular oxygen from various atmospheres. Forthis purpose, it is desirable to chose a salt which has a high oxygenaffinity (low half-saturation partial pressure of oxygen) in order thatthe salt will extract the greatest possible amount of oxygen from theatmosphere to be scavenged. In order to effect removal of oxygen from agaseous mixture, and thus to scavenge the mixture, it is only necessaryto expose a salt of Formula XVII or XVIIA (and some of the instantcompounds are soluble and stable in solution) to the gaseous mixture tobe scavenged. As those skilled in the art are well aware, to effect themaximum possible scavenging of oxygen from the gas, it is essential thatintimate control between the gas and scavenging salt be achieved. Suchintimate contact may be achieved, for example, by spraying a finelydivided jet of a liquid solution of the salt through a stream of the gasto be scavenged, by bubbling the gas through the liquid solution or byallowing the liquid to flow down a tower packed with inert, granularmaterial while the gas to be scavenged flows up the tower.

A closely-related utility of the salts of Formulae XVII and XVIIA istheir use in determining the amount of molecular oxygen present in anoxygen-depleted atmosphere. The formation of an adduct between thecation of the salt and oxygen changes the spectrum of a solution of thesalt. Therefore upon passing a beam of light or other electromagneticradiation through the salt solution, the absorbance of which differs asbetween the free cation and the oxygen adduct, the proportion of thesalt in the adduct form, and hence the equilibrium constant may bedetermined. The relationship between the equilibrium constant, partialpressure of molecular oxygen in the system and the color change, asmeasured spectrophotometrically, is indicated by the following equation:##EQU1##

In equation 1, A-Ao represents the change in absorbance that occurs fora given total concentration of the dry cave complex cation, [Complex],and the partial pressure of molecular oxygen, (P_(O).sbsb.2). K is theequilibrium constant for O₂ adduct formation, E _(adduct) and E_(complex) are molar extinction coefficients for the O₂ adduct and forthe dry cave complex, respectively. By way of example, for a cobalt drycave complex, typical parameters are E_(adduct) -E_(complex) =250,K_(O).sbsb.2 =1 torr⁻¹ and total concentration of [Complex]=10⁻³ M. Forthis case, and making the modest assumption that α A can be measured towithin an accuracy of 0.02 units, P_(O).sbsb.2 can be measured directlyover the range of from about 0.09 torr to about 12 torr. By choosing asystem in which K_(O).sbsb.2 =5 torr⁻¹ with the other parametersremaining about the same, the measurable range is from about 0.02 torrto 2.3 torr. Moving in the other direction, for K_(O).sbsb.2 =0.1 torr⁻¹and under otherwise equivalent conditions, the measurable range ofP_(O).sbsb.2 is from 0.87 torr to 115 torr. Thus, it is readily apparentthat the salts of the present invention have excellent flexibility inthe determination of the molecular oxygen concentration present inoxygen-depleted atmospheres. Furthermore since the instant salts can beused in a liquid solution, they may be useful in situations whereintroduction of the oxygen-measuring instruments would be difficult orimpossible. For example, a solution of an instant salt could beintroduced into a location within an animal or human body where it isdesirable to measure the oxygen concentration and the colorimetricmeasurement made by means of an optic fiber endoscope.

However, by far the most important utility of the salt of Formula XVIIand XVIIA lies in their use in separating oxygen from air (or any otherreadily-available and cheap source of oxygen-containing gas). Theessential requirement for a compound to be used for separating oxygenfrom air is that the compound must load and unload molecular oxygenreversibly at appropriate partial pressures of molecular oxygen; giventhe present cost of producing the salts of Formulae XVII and XVIIA (andindeed of all other oxygen-complexing compounds known) and therelatively low value per unit weight of the molecular oxygen which isthe end product of the process, from an economic standpoint it isessential that an oxygen-complexing compound be able to undergo manyoxygen complexing/decomplexing cycles without destruction, and it is animportant advantage of the salts of Formulae XVII and XVIIA that theycan undergo an extremely large number of such oxygencomplexing/decomplexing cycles.

Contact between the salt of Formula XVII or XVII A and theoxygen-containing gas may be effected in a number of different ways. Thesalt may be used in the solid phase; for obvious reasons, if it isdesired to use the salt in the solid phase, this solid phase ispreferably in a finely divided form so as to expose a large surface areato the oxygen-containing gas and may, for example, be in the form of athin coating upon an inert substrate such as finely-divided silica orsome other similar material having a large surface area. Alternatively,the salt may be used in the liquid phase, either in the form of a truesolution, a colloid or a dispersion; such a dispersion might be in theform of a slurry. Finally, the salt may be attached to a supportingsolid; as already indicated, the salt may be in the form of a thin layeron an inert substrate but the salt may also be chemically bonded to thesubstrate. A convenient form of substrate to which the salt may bechemically bonded is a synthetic polymer provided with substituentssusceptible to nucleophilic attack, for example a crosslinkedpolystyrene polymer containing benzyl chloride functional groups. Onepossible method for attaching the salts of Formula XVII or XVII A tosuch a polymer involves reaction of a salt in which the two groups R₄are hydrogen atoms with the polymer containing the functional groups; itis believed (although the invention is in no way limited to this belief)that in most cases the two primary or secondary amine groups NR₄ R₆react with separate, spaced functional groups on the polymer therebycausing the four central nitrogen atoms coordinated to the metal atom tolie in a plane approximately parallel to the plane of the polymersurface and thereby creating a cavity between the metal atom and thepolymer surface in which the oxygen or similar molecule can beaccommodated. Alternatively, one may use a polymer having pendant group(e.g. pyridyl) capable of acting as an axial ligand Z and treating thispolymer with a salt of Formula XVII, thereby allowing the pendant groupsto coordinate with the metal atoms in the salts and binding the salts tothe polymer.

It will of course be appreciated that, where it is desired to chemicallybond a salt of Formula XVII A to a support, it may be more convenient toeffect reaction between a salt of Formula XVII and the support, and thento pass a material appropriate to supply the desired ligand Z over thesupport. Furthermore, in many cases it may be more convenient to use thenickel or other relatively unreactive salt of Formula XVII, or ademetallated form of the salt of Formula XVII, in the reaction with thesupport, and then to carry out the insertion of the desired active metal(and, if desired, insertion of the ligand Z) thereby generating thedesired salt of Formula XVII or XVII A in situ on the support.

As already mentioned, to be useful in separating oxygen from air in apractical process, the oxygen complexing compound must load and unloadmolecular oxygen at appropriate partial pressures thereof, and thisability can be evaluated on the basis of the equilibrium constant forthe reaction:

    Complex+O.sub.2 ⃡Complex(O.sub.2)              (2)

where "Complex" represents the cationic metal complex of a salt ofFormula XVII or XVIIA. In most practical processes for the separation ofoxygen from air, the salt will be allowed to take up molecular oxygen incontact with air under approximately atmospheric pressure (in order toavoid the large energy consumption needed to compress the volumes of airinvolved), and the oxygen partial pressure in the atmosphere isapproximately 160 torr. The oxygenated salt will normally give up itsoxygen to a chamber at a pressure of about 10 to about 50 torr, andsince the gas given off will be reasonably pure oxygen the oxygenpartial pressure in the chamber will have substantially the same value.Obviously, in order to extract the maximum amount of oxygen per pass ofa given quantity of salt through the process, it is desirable that thepercentage saturation of the salt with oxygen show the maximumdifference for the oxygen partial pressures used for loading andunloading oxygen in the process. Table 1 below shows the degrees ofsaturation for various values of the equilibrium constant for a loadingoxygen partial pressure of 160 torr and off loading oxygen partialpressures of 50 and 10 torr, together with the percentage difference insaturation (shown below the symbol Δ) at 160 torr as compared with 50and 10 torr respectively.

                  TABLE 1                                                         ______________________________________                                        Percent Saturation, oxygen partial pressure                                   Equilibrium                                                                   constant                                                                      .sup.K O.sub., torr.sup.-1                                                               160 torr   50 torr(Δ)                                                                        10 torr(Δ)                              ______________________________________                                        0.3        98         94     (4)  75    (23)                                  0.1        94         83     (11) 50    (44)                                  0.03       83         60     (23) 23    (60)                                  0.01       62         33     (29) 9     (53)                                  0.003      32         13     (19) 3     (29)                                  0.001      14         5      (9)  1     (13)                                  ______________________________________                                    

It will be seen that a reasonable amount of oxygen separation can beachieved with salts having an equilibrium constant in the range of about0.003 to about 0.1 torr, and that the optimum equilibrium constant isabout 0.01 to about 0.03 torr. Naturally, the equilibrium constantvaries considerably with temperature and thus in choosing an appropriatesalt for any given process, it is important to take into account thetemperature at which the process will be operated.

The foregoing discussion has assumed that the loading and unloading ofoxygen from the salt solution is effected at the same temperature, i.e.that the oxygen separation process is effected isothermally, but ofcourse the process may be operated so that off-loading of oxygen fromthe salt is effected at a higher temperature than loading of the oxygen.Since the equilibrium constant of the salts of Formulae XVII and XVIIAdecreases relatively quickly with temperature, the amount of oxygenseparated per pass of any given quantity of salt through an oxygenseparation process can be increased by unloading the oxygen at a highertemperature than that at which the oxygen is loaded. For example,compound number 32 (see Tables 2 and 3 below) has an equilibriumconstant of 0.3 torr at 0° C. and an equilibrium constant of 0.003 torrat +30° C., so loading with molecular oxygen at 0° C. gives 98%saturation at 160 torr oxygen partial pressure while off-loading at 30°C. and 50 torr leaves only 13% saturation, a difference of 85%. However,when using non-isothermal processes, account will of course have to betaken of the energy consumed in warming and cooling the salt solutionduring the process.

The oxygen affinity of the salts of Formulae XVII and XVIIA can becaused to vary over at least five orders of magnitude depending on thenature of the substituent groups attached to the complex and the solventin which the complex is dissolved or dispersed. It is particularlyimportant that this binding affinity can be tuned to values close tothose that may be desired for specific applications. For example, thesalt of Formula IA having R₁ =H, R₂ =R₃ =R₄ =CH₃, R=hexamethylene,X=Y=trimethylene, and Z=N-methylimidazole, in aqueous solution hasP_(1/2)(0.sbsb.2.sub.) =0.625 torr at 20° C. This value of thehalf-saturation partial pressure is very close to that of humanmyoglobin at the same temperature (P_(1/2)(0.sbsb.2.sub.) =0.667 torr atpH 8). In contrast, at the same temperature but in acetonitrile solvent,the complex differing only in that X is an ethylene group, has a valueof P_(1/2)(0.sbsb.2.sub.) =2.13 torr, which is quite close to theequilibrium constant of human hemoglobin (P1/2(0.sbsb.2.sub.) =2.50 torrat pH 8). Thus, the dry cave complexes can be useful when molecularoxygen must be made available at a precise partial pressure. Obviously,those salts of Formulae XVII and XVIIA having equilibrium constantsclose to those of mammalian hemoglobins can be used to load oxygen inthe lungs of a mammal and to unload oxygen in the non-lung tissues ofthe mammal, i.e. the salts can be used as a synthetic blood. Naturally,when a salt is to be used for this purpose it is essential to select asalt which will not be toxic to the mammal in which the synthetic bloodis to be employed and which can be broken down and excreted from themammal's body without injury to its metabolic systems.

FIG. 4 of the accompanying drawings shows an experimental apparatuswhich can be used for separating oxygen from air on a small scale. Thisapparatus, generally designated 10, comprises an air inlet vessel 12 inthe form of a three-necked, 500 ml. flask 12 which is equipped with anoutlet tube 14 at its base. The flask 12 is surrounded by a liquidcontainer 16 containing a liquid 18 which serves to maintain the flask12 at constant temperature. The outlet tube 14 passes through the baseof the container 16 in a fluid-tight manner.

One neck 20 of the flask 12 is connected via a stop-cock 22 to a source(not shown) of air under slight pressure. The central neck 24 of theflask 12 is similarly connected via a stop-cock 26 to an air outlet(which may be simply a tube open to the air, as shown in FIG. 4). Thethird neck 28 of the flask 12 is connected via a tube 30 and a stop-cock32 to a tube 34, which extends from one neck 36 of an outlet flask 38 toa position near the base of this flask. The outlet flask 38 is athree-necked, 250 ml. flask disposed within a container 40 containing anappropriate liquid 42 which functions in the same manner as the liquid18 surrounding the inlet flask 12, thereby holding the outlet flask 38at a constant temperature.

The outlet tube 14 extends from the inlet flask 12 through a stop cock44, a connecting stop 46 and a three-way valve 48 to a second neck 50 ofthe outlet flask 38. A side limb 52 attached to the three-way valve 48is connected to a monometer and vacuum pump (neither of which is shown).The third neck 54 of the outlet flask 38 is closed by means of a sampletube 56 equipped with a stop-cock 58. Finally, an ultrasonic cleaningdevice, indicated schematically at 60, is disposed within the liquid 42surrounding the outlet flask 38.

To use the apparatus shown in FIG. 4 to separate molecular oxygen fromair, isopropanol at -40° C. is used as the liquid 18 surrounding theinlet flask 12, while water at 30° C. is used as the liquid 42surrounding the outlet flask 38. After ensuring that the stop-cock 44 isclosed, a solution 62 of a compound of the invention is placed withinthe inlet flask 12, the stop-cocks 22 and 26 are opened and thestop-cock 32 closed. Air is then blown through the stop-cock 22, theneck 20 and a gas inlet tube 64 extending from the neck 20 of the inletflask 12 to adjacent the base of this flask, the lower end of this gasinlet tube 64 being provided with a gas dispersion frit 66. The passageof air through the tube 64 into the solution 62 is continued until thesolution 62 becomes substantially saturated with oxygen; during thispassage of air through the solution 62, the open stop-cock 26 serves asan outlet for excess air. While the air is thus being passed through thesolution 62, the three-way valve 48 is disposed so as to allowcommunication between the side limb 52, the tube 46 and the outlet flask38; the stop-cock 58 is held open so as to permit fluid communicationbetween the sample tube 56 and the outlet flask 38. Thus, the vacuumpump attached to the side limb 52 evacuates the tube 46, the outletflask 38 and the sample tube 56.

After the solution 62 has become saturated with oxygen, the valve 48 isadjusted so as to permit fluid communication between the tube 46 and theoutlet flask 38, but to cut off both this tube and flask from the sidelimb 52. The stop-cock 44 is then opened, whereupon the low pressure inthe flask 38 transfers the solution 62 from the inlet flask 12 via thetube 46 through the outlet flask 38. After about 95% of the solution 62has been removed from the inlet flask 12, the stop-cock 44 and the valve48 are closed completely. The ultrasonic cleaning device 60 is thenoperated to ensure good evolution of molecular oxygen from the solution62 (which is now in the outer flask 38); the oxygen thus evolved entersthe sample tube 56 and may also if desired may be removed by the sidelimb 52. After evolution of molecular oxygen has ceased, the stop-cock22 is closed and the stop cock 26 connected to a vacuum pump therebyevacuating the inlet flask 12 and the tube 30 (it will be recalled thatthe stop-cocks 32 and 44 are closed). If it is desired to retain asample of the gas evolved for mass spectrometric or gas chromatographicanalysis, the stop-cock 58 is now closed, thereby isolating the gassample in the sample tube 56. Next, the stop-cock 32 is open, whereuponthe low pressure in the tube 30 and the inlet flask 12 causes thesolution 62 to be recycled from the outlet flask 38 to the inlet flask12; the stop-cock 32 should be reclosed before the level of the solution62 in the outlet flask 38 falls below the lower end of the tube 34. Theapparatus is now ready to carry out another cycle.

Although the apparatus just described is suitable for separating oxygenfrom air on a very small scale, for commercial purposes it will probablybe found more satisfactory to employ an immobilized liquid membraneapparatus to effect such separaton; details of appropriate methods offorming such liquid membranes are described in the references alreadylisted above.

The usefulness of such immobilized liquid membranes is however, notconfined to separating molecular oxygen from air. Since such membranesare selectively permeable to molecular oxygen, they are useful insituations where it is desired to transport molecular oxygen into acontainer without allowing egress of other compounds from the container.For example, the limiting factor on the life of zinc/air batteries isoften escape of water vapor from the battery through passages designedto allow entrance of oxygen into the battery, rather than exhaustion ofanode material. By using an immobilized liquid membrane containing asalt of the invention, molecular oxygen can enter the battery withoutwater vapor escaping therefrom, thus increasing the life of the battery.

Finally, certain salts of Formulae XVII and XVIIA, and in particular thecobalt salts, show promise as possible catalytic, possiblestoichiometric promoters of oxidation reactions in which atmosphericoxygen serves as the oxidizing agent. For such use, the bridging groupsmay be viewed as possible substrates for such oxidations. Thus, theinstant salts might be used in zinc/air batteries to increase theconcentration of molecular oxygen in the electrolyte and thereforeincrease the flux of cathode material to facilitate higher dischargerates. When the salts are to be used catalytically, it may be especiallyadvantageous to bond them chemically to a support. Further, thecomplexes may exhibit a buffer-like action in generating a desiredpartial pressure of molecular oxygen and may find wide use as anelectrode coating where the complexes may facilitate the reduction ofoxygen to water or the anodic formulation of molecular oxygen fromwater, e.g. on the cathodes of zinc/air batteries.

As already mentioned, the invention extends to the nickel salts ofFormulae II, III, XVIII, IIA, IIIA, and XVIIIA. As described in moredetail below, these nickel salts are useful as intermediates for thepreparation of the corresponding complexes containing other metals.

Methods will now be described for synthesis of the salts of FormulaeXVII and XVIIA. It will be appreciated that the exact synthetictechniques employed may vary somewhat with the exact substituents in thecationic metal complexes; for example, where one of the substituentscontains a reactive group, it may be necessary to protect the reactivegroup during certain stages of the synthesis. Furthermore, the exacttechniques needed for isolation and purification of the salts may varyconsiderably depending upon the exact salt employed. However, thenecessary variations in synthetic techniques are believed to be apparentto those skilled in the art or easily discoverable by the routineempirical techniques employed by skilled chemists in preparing newcompounds. As mentioned above, in the salts of Formula XVII and XVIIA,it does not appear to be possible to prepare pure cobalt salts having atetrachlorozincate anion, while in the case of the salts of FormulaXVIIA having iron as the metal ion, it appears that if chloride ispresent in the reaction mixture used to prepare the ion complex, thechloride tends to prefer to enter the cation as the ligand Z inpreference to remaining as the anion. It will also be apparent to thoseskilled in the art that certain combinations of the groups R₄ and R₆ maycause electronic and steric hindrances during the preparative processwhich may make salts having these combinations of R₄ and R₆ difficult toprepare by certain synthetic routes. Finally, it is probable that thoseskilled in the art will be able to devise different syntheses of thesalts of Formulae XVII and XVIIA and it should be noted that theinvention is not limited to any particular method for the synthesis ofsuch salts.

The preferred synthesis of the salts of the present invention proceedsfrom the "Jager" complexes prepared as described by Jager in Z. Anorg.Allg. Chem., 346, 76 (1966) and Z. Chem., 8, 30, 392 (1968). Additionalpublished definitive syntheses of the Jager complexes can be found inthe following publications: Dennis E. Riley and Daryle H. Busch,Inorganic Synthesis, 18, 36 (1978) and Jerome Streeky, Thesis, The OhioState University, Columbus, Ohio (1979). The Jager complexes may berepresented by Formula V shown in FIG. 3 of the accompanying drawings.

The first step in the synthesis of the instant salts involves conversionof the acyl groups of the Jager complex to methyl vinyl ether groups asreported by P. W. R. Corfield, J. D. Mokren, C. J. Hipp, and D. H.Busch, Journal of the American Chemical Society, 95, 4465 (1973); theproducts of this reaction are of Formula VI shown in FIG. 3 of theaccompanying drawings. Reagents useful in this reaction include not onlythe CH₃ SO₃ F shown in FIG. 3 but also for example trialkyloxoniumcations (R₃ 0⁺). As reported by Corfield et al vide supra, primary andsecondary amines HNR'R" readily displace the methoxy group from themethyl vinyl ether grouping in the compounds of Formula VI to producethe compounds of Formula VII, which contain the macrocyclic ligand ofthe salts of the present invention. This ligand has a serendipitousarrangement of atoms and electrons such that good metaldioxygen carriersare formed.

The second major aspect of the synthesis of the salts of the presentinvention involves bridging of the compound of Formula VII to form abicyclic compound of Formula I or a tricyclic compound of Formula II. Atthis stage compounds of Formula III can already have their carbon-carbonbridge from a variant synthesis of the Jager complex which will bedescribed in detail below. A salt of Formula I can be formed most easilyby one of two routes. The first synthesis route involves the reaction ofthe methyl vinyl ether intermediate of Formula VI with an appropriateα,ω-diamine containing R. This reaction parallels the reaction detailedabove for synthesizing the ligand of Formula VII from the methyl vinylether intermediate of Formula VI and is a very general reaction whichcan be applied to almost any diamine. Additional information on thisreaction route can be found in the following publication: WayneSchammel, Thesis, The Ohio State University, Columbus, Ohio (1976). Thisreaction route will also be illustrated in the examples which follow.

The second route for synthesizing the metal dry cave complex of FormulaI is often more useful since it does not require the existence of adiamine, but rather a diol or dihalide is adequate. For this route, acompound of Formula VIII is prepared in which at least one substituenton each nitrogen atom is hydrogen. The reaction of this compound withthe ditosylate of a diol or with a dibromide, or similar reagent,readily yields the desired bridged compound of Formula IX, as shown inFIG. 3. Additional useful reagents for this reaction include brosylates,nosylates, mesylates, oxonium ions, alkyl perchlorates, alkylfluorosulfonates, and the fluorinated compounds, triflates, nonaflates,tresylates, and the like.

The synthesis of a compound of Formula III differs from the two reactionroutes outlined above for the formation of a compound of Formula I inthat formation of a bicyclic structure precedes conversion of the Jagermacrocycle of Formula V into the neutral ligand of Formula VII. Avariant of the Jager complex having a bicyclic structure serves as thestarting material in this synthesis route. For preparation of thestarting material, reference is made to the following publication: J.Eilmes and E. Sledziewska, Bulletin De L'Academie Polonaise DesSciences, Serie Du Sciences Chemique XXVI, No. 6, 441 (1978). Thereaction procedure for synthesis of compound of Formula III can bevaried at an intermediate step in the procedure for synthesizing eithera compound of Formula III or a doublebridged compound of Formula II. Thereaction procedure commences with a compound of Formula X, aneutralized, deacylated species of the Jager macrocycle (see Example IVfor further details on synthesis of this species). As shown in FIG. 3this compound of Formula X is reacted with a dicarbonyl halide or thelike to introduce the R₅ bridge group, thereby producing a compound ofFormula XI. This compound of Formula XI can have its carbonyl groupconverted to a methyl vinyl ether group in a manner described above forpreparation of a compound of Formula VI and the methyl vinyl ether groupthen replaced by an amine group in the manner described above forpreparation of a compound of Formula VII, thus synthesizing a compoundof Formula III. Alternatively, a diamine can be added to the methylvinyl ether functional complex to introduce an R bridge and thussynthesize a compound of Formula II.

The original Jager complexes described in the papers mentioned above aresubstituted such that the compounds of Formula XVII produced therefromhave the groups R₁ hydrogen atoms and the groups R₂ methyl groups.Compounds in which both such groups are hydrogen atoms may be preparedby the methods described in Hiller, Dimroth and Pfitzner, Liebigs Ann.Chem. 717, 137 (1968); this paper also describes starting materialssuitable for preparing compounds of Formula XVII in which X and Y areo-phenylene groups. Starting materials suitable for producing compoundsof Formula XVII in which R and R₂ are both methyl groups are describedin Tang et al, Inorganic Chemistry, 12, 2589-95 (1973); this paper alsodiscusses techniques for varying the length of the carbon chain in thegroups X and Y in Formula XVII.

In all of the foregoing illustrative syntheses, the use of anyparticular substituent is strictly for purposes of illustrating thepresent invention and is not a limitation of the present invention. Alsoan oxidation state (valence) of two for metal A has been arbitrarilyselected herein for illustration and instructional purposes and is notintended to be a limitation of the present invention. The organic partof the cations of the instant salts generally are synthesized on arelatively unreactive metal ion such as nickel or zinc, nickel being thepreferred metal for this purpose. Some copper compounds of Formulae XVIIcan be synthesized with the copper already in place. Once the ligandstructure has been correctly synthesized with a relatively unreactivemetal ion, that metal ion is removed and the ligand is coordinated to amore reactive metal ion. The relatively unreactive metal ion can beremoved by the addition of dry HCl to an acetonitrile solution of thecompound first prepared. The addition of ZnCl₂ then results inseparation of the solid tetrachlorozincate salt. Before reaction withthe desired reactive metal ion, the ligand tetrachlorozincate saltpreferably is converted to the hexafluorophosphate salt, by reactionwith a soluble hexafluorophosphate e.g. ##STR4## Alternatively, thehexafluorophosphate salt can be isolated directly, after separation ofthe ligand from the relatively unreactive metal ion by HCl, uponaddition of NH₄ PF₆, as illustrated below. ##STR5##

(Although the formula of the demetallated hexafluorophosphates has beenwritten above as LH₃ (PF₆)₃, our latest experiments indicate that, in atleast some cases, a chloride anion may be present along with thehexafluorophosphates so that the formula may be more correctly given asLH₄ Cl(PF₆)₃. However, it will be appreciated that this uncertainty asto the formula of the demetallated intermediate makes no difference inthe practice of the preparative method, and does not extend to theformula of the instant metallated salts produced as described below.) Asalready mentioned, it has not been possible to prepare purechlorozincate salts of Formula XVII where the metal is cobalt. Thus, forexample, in preparing cobalt(II) complexes, the ligandhexafluorophosphate salts, LH₃ (PF₆)₃, slurried in methanol may haveadded thereto a solution of sodium acetate and cobalt(II) acetatetetrahydrate in methanol: ##STR6## The compounds must be prepared in theabsence of oxygen. The four coordinate complexes separate from solution.Alternatively, additional ligand salts and solvents which can be used inremoving the unreactive metal ion and replacing it with a desiredreactive metal ion include the perchlorate, hexafluoroarsenate,fluoroborate, trifluoromethylsulfonate, or halide salts; and assolvents, nitriles, alcohols, nitroalkanes, or water.

The salts of Formula XVIIA, which tend to have a stronger oxygenaffinity than the corresponding salts of Formula XVII, may be preparedfrom the corresponding compounds of Formula XVII. Usually, it is onlynecessary to dissolve the salt of Formula XVII in a solution containingthe desired axial ligand Z to form the corresponding compound of FormulaXVIIA. Suitable solvents for carrying out such reactions includemethanol, acetone and other ketones, acetonitrile and other nitriles,dimethylformamide and other amides, sulfoxides, sulfones, and the likeand mixtures thereof.

This reaction is illustrated below. ##STR7##

Since the compounds of Formula XVIIA differ from the compounds ofFormula XVII only in the presence of the ligand Z, interconversion ofthe two groups of compounds can occur readily in solution, and there issome reason to believe than in many cases in which a compound of FormulaXVII is used in solution, the species present may in fact be a compoundof Formula XVIIA having a molecule of the solvent as the axial ligand.For example, it is likely that many of the compounds of Formula XVIIexist in aqueous solution in the form of the corresponding compound ofFormula XVIIA with a molecule of water as the ligand Z, even thoughcrystalization of the salt from aqueous solution may take place in theform of the water-free salt of Formula XVII. Accordingly, the oxygenaffinities measured for the salts of Formula XVII and XVIIA will oftenvary with the solvent used, since the choice of solvent may affect theligand Z in the cation.

Oxygen-Binding Polymers Having Attached Thereto Bridging Groups ofFormulae XIX or XIX A, or Molecules of Formula XIX B

As mentioned above, the groups of Formula XVII and XVIIA may be usedchemically bonded to a substrate such as a synthetic polymer. Rathersurprisingly, I have found that groups of Formula XIX and XIX A, whichare unbridged analogs of the compounds of Formulae XVII and XVIIArespectively, also complex molecular oxygen reversibly when chemicallybonded to a support although the free forms (wherein hydrogen atoms areattached to the NR'₆ groups) of the corresponding complexes bondmolecular oxygen largely irreversibly. I believe (although the inventionis in no way limited by this belief) that the reason for this differenceis that the irreversible decomposition of the free complex proceeds viaa mechanism which requires close conjugation of two free complexes in aparticular spatial arrangement, and that the chemical bonding of thecomplex to a substrate prevents two molecules of the complex comingtogether in the arrangement needed for the irreversible decomposition.

The synthesis of the unbridged compounds needed for synthesis of theoxygen-binding polymers of the invention will be apparent to thoseskilled in the art from the foregoing description. The nickel analogs ofthe free unbridged complexes are the compounds of Formula VII in whichat least one of R' and R" is hydrogen, and the preparation of suchnickel analogs has already been described above. The nickel analogs ofFormula VII may be reacted with the polymer and the nickel then replacedwith a more active metal in the manner already described. Alternatively,the compound of Formula VII may have the nickel replaced with a moreactive metal, and the resultant compound thereafter reacted with thenickel. Methods for the attachment of the compounds to the polymers aredescribed in Examples 213-14 below. The unbridged compound isdeprotonated with a base, such as methoxide, and a solution of adeprotonated compound allowed to flow through the resin, whereupon thedeprotonated compound reacts with the polymer to form the bridginggroups of Formula XIX or XIX A. Obviously, if it is desired to produce apolymer containing bridges of the Formula XIX A, insertion of the ligandZ may be affected as already described either before or after reactionof the free complex with the substrate.

In the polymers of the invention incorporating molecules of Formula XIXB, electron-donating groups on the polymer coordinate with the metalatom so that the electron-donating group in effect functions as a fifthligand in a manner similr to the ligand Z in the compounds of Formulae IA-XVIII A. However, since the electron-donating group is fixedlyattached to the polymer, the effect of its coordination to the metalatom is to attach the molecule of Formula XIX B to the polymer.Appropriate electron-donating groups include, for example, pyridyl andamino groups.

The polymers containing molecules of Formula XIX B may be prepared, asillustrated in Example 214, simply by passing a solution of theappropriate salt through the polymer.

Compounds of Formula XX

The effectiveness of the bridges in providing oxygen-complexingproperties in the compounds of Formulae XVII and XVIIA, coupled with thefact that it is known that oxygen-complexing ability in such compoundsis due to the provision of a hydrophobic cavity in which the oxygenmolecule can rest, led to the discovery that, by adding similar bridgesto other known types of macrocyclic compounds, such compounds can alsobe endowed with oxygen-complexing properties. These newoxygen-complexing compounds comprise the compounds of Formulae XX toXVI. Although some of Formulae XX to XVI are shown in the accompanyingdrawings in their demetallated forms, in all cases the invention extendsto the complexes of such demetallated forms with nickel, cobalt, iron,copper or manganese ions in the +2 or +3 oxidation states and (exceptfor the pentadentate compounds of Formula XXV) to such metal compoundspossessing a fifth, axial ligand, which may be any of the ligands Zdefined above with reference to Formula XVIIA.

The compounds of Formula XX may be prepared from 2,4-pentanedione, theappropriate alpha, omega-dihalide incorporating the group R₇, and theappropriate alpha, omega-diamine, H₂ NR₈ NH₂. The 2,4-pentanedione istreated with alkali metal to produce the 3-metallo derivative. Reactionof this metallo derivative with the alpha, omega-dihalide, Hal-R₇ -HAL,produces the tetraketone shown in FIG. 7, which is then condensed withthe alpha, omega-diamine, in for example ethanol, to produce thecompound of Formula XX. This synthesis is similar to the synthesis ofprior art compounds having much shorter bridges but which do notreversibly complex oxygen, as described in the following papers:

Crumbliss et al, Science, 164, 1168 (1969), and J.A.C.S., 92, 55 (1970)

Pignatello et al, J.A.C.S., 101, 5929 (1970)

Wallace et al, J. Biol. Chem., 257, 4966 (1982)

Hoffman et al, J.A.C.S., 92, 61 (1970) and 97, 673 (1975).

Compounds of Formula XXI

The compounds of Formula XXI are bridged derivatives of the well knownanhydrotetramer of o-aminobenzaldehyde (TAAB). It has previously beenshown that TAAB will add nucleophiles across two imine linkages to formbridged compounds, so that to produce the compounds of Formula XXI it isonly necessary to react the appropriate dinucleophile with TAAB. Thedinucleophile may be, for example, the dianion of a diol, dithiol ordiamine or a carbon dinucleophile such as a dialkali metal alkyl or anenamine. If desired, the nucleophile used may contain additionalfunctional groups to give structures able to undergo additionalreactions. For example the nucleophile1-(N-pyrrolidine)-1-phenylethylene may be used.

Details of the synthesis of TAAB and the manner of adding nucleophilesthereto, together with procedures for inserting metal atoms therein, aredescribed in the following publications:

Goedken et al, J. Coord. Chem., 7, 89 (1977)

Taylor et al, J.A.C.S., 91, 1072 (1969)

Katovic et al, Inorg. Chem., 10, 458 (1971), and J.A.C.S., 91, 2122(1969)

Kamenar et al, Inorg. Chem., 18, 815 (1979)

Madden, I. L., Ph.D. Thesis, The Ohio State University, (1975).

Compounds of Formulae XXIIA-XXIIE

These compounds are derivatives of the saturated tetraazamacrocyclescyclam, cyclen and their congeners. The bridging groups R₁₀ may beinserted by reacting the unbridged macrocycle (in which each nitrogencarries a single proton) with an appropriate alpha, omega-dihalide ordipseudohalide, such as a ditosylate. As with the other groups ofcompounds discussed above, insertion of the metal atom (and if desiredthe axial ligand) is effected in the same way as of compounds FormulaeXVII and XXI; basically, it is only necessary to mix solutions of thecompound of Formula XXII and an appropriate metal salt and then, ifdesired, to add the appropriate ligand Z.

Further details of appropriate conditions for carrying out the bridgingreaction to produce compounds of Formula XXII are given in the followingpapers:

Barefield and Wagner, Inorg. Chem., 12, 2435 (1973) and 15, 408 (1976)

Ramasubbu et al, J. Chem., Soc., Chem. Commun., 1982, 277

Wainwright, J. Chem. Soc., Dalton Trans., 1980, 2117.

Compounds of Formula XXIII

The compounds of Formula XXIII are produced by a reaction which isgenerally similar to that described above for producing the compounds ofFormula XXI and involves the addition of an alpha, omega dinucleophileto the azomethine groups in the known starting material shown in FIG. 7.Appropriate methods for carrying out reactions of this type aredescribed in:

Taylor et al, J. Am. Chem. Soc., 91, 1072 (1969)

Keypour and Stotter, Inorg. Chim. Acta. 33, L149 (1979)

Insertion of the metal atoms and, if desired, the ligand Z may beeffected in the manner already described above in relation to compoundsof Formula XXI.

Compound of Formula XXIV

The insertion of the bridges, metal atoms and (optionally) the ligands Zmay be effected in ways precisely analogous to those already describedabove for compounds of Formula XXII. Further discussion of appropriatereaction conditions may be found in the three papers cited above withreference to the compounds of Formula XXII.

Compounds of Formula XXV

The compounds of Formula XXV may be regarded as derivatives of thewell-known "salen" ligand (1,6-bis(2-hydroxyphenyl)-2,4-diazahexa-1,5-diene). As shown in FIG. 7, thecompounds of Formula XXV are prepared by Schiff base condensation of adiamine with the appropriate triamino-dialdehyde. The preparation of thedialdehyde may be carried out by slight modifications of the synthesisdescribed in the following papers:

Green et al, J. Chem. Soc. Chem. Commun. 1968, 518 and Inorg. Chim.Acta, 5, 17 (1971)

Black and Lane, Aust. J. Chem., 23, 2039 (1970)

Lindoy and Busch, Inorg. Nucl. Chem. Lett., 5, 525 (1969)

Fleischer et al, Inorg. Nuc. Chem. Lett., 9, 10610 (1973).

The preparation of the diamine starting material may be carried out bythe method described in Martin et al, J. Chem. Soc., Dalton Trans.,1979, 1497 and 1503.

Insertion of the metal atoms into the compounds of Formula XXV may bemade in the manners already described above with reference to othercompounds of the invention. It should be noted, that unlike the othercompounds of the invention already described, the compounds of FormulaXXV are pentadentate; the four central nitrogen atoms complex the metalion in the usual square planar arrangement, while the NR₁₃ groupcomplexes the metal ion axially. Accordingly, the compounds of FormulaXXV will not simultaneously complex both an oxygen molecule and a ligandZ.

Compounds of Formula XXVI

The compounds of Formula XXVI are closely related to the well knowncobalt (II) complexes of dimethylglyoxime, and the compound in which R₁₅is a (CH₂)₁₂ groups is described in papers in Helv. Chim. Acta, 54, 2747and 2753 (1971). The other compounds of Formula XXVI may be prepared inmanners exactly analogous to the synthetic procedure described in thefirst of these two papers.

As already mentioned, the compounds of Formulae XX to XXVI complexoxygen and may thus be used in any of the ways already described inrelation to compounds of Formula XVII and XVIIA.

Numerous examples of compounds of the invention and intermediates usefulin preparing such compounds will now be given, though by way ofillustration only, and such examples should not be construed aslimiting. All units are in the metric system unless otherwise expresslyindicated and all references cited herein are incorporated herein byreference.

In view of the complexity of the chemical nomenclature necessary todescribe the instant salts and the intermediates used to prepare them,for brevity there are set out in Table 2 below the formal names of allcompounds prepared in the following examples, together with numbers bywhich the compounds are identified in later tables. It should be notedthat the nomenclature used in Table 2 differs in certain respects fromthat used in the examples of my aforementioned parent application, Ser.No. 114,670. In particular, in the aforementioned parent application theattachment of the four nitrogen atoms to the metal ion was indicated bythe nomenclature ". . . N₄)cobalt (II) . . . ", and similarly for othermetals; in Table II, and elsewhere in the following examples, the morecorrect nomenclature (. . . κ⁴ N)cobalt(II) . . . " is employed instead.Rather more importantly, some of the examples in my aforementionedparent application use a slightly erroneous numbering system which hasbeen corrected in the nomenclature used in Table 2; where such incorrectnomenclature was previously employed, the name originally given for thecompound in the example is included in parentheses following "formerlydesignated".

Table 3 below sets out the various substituents in those compound listedin Table 2 which fall within Formulae I and IA; obviously, where nosubstituent value is given in the column for the ligand Z, the compoundis of Formula I, while when a value is given for Z the compound is ofFormula IA. In those cases where Z is stated in Table 3 to be carbonmonoxide followed by another ligand, the compound actually prepared isthe carbon monoxide adduct of the salt of Formula IA, so that the carbonmonoxide is actually within the dry cave of the cation metal complex andthe other ligand mentioned occupies the Z position. Similarly, where twoidentical ligands Z are stated in the present (as in compound No. 22,where Z is stated to be (NCS)₂), one of these ligands resides within thedry cave and the other occupies the normal Z position. In Table 3, "Py"denotes pyridine and "IM" designates imidazole. To improve legibility,the usual minus signs are omitted from the anions, and thus it should benoted that in Table 3 (and in Tables 4, 5 and 6) "Cl" denotes a chlorideion, not a free chlorine atom. In a few cases, demetallated compoundsare produced; these compounds are indicated in Table 3 by a dash in theM^(n).spsp.+ column.

Table 4 lists the identities of the variable groups and substituents ofthe various compounds listed in Table 2 which fall within Formula II,Table 5 similarly lists the corresponding values of the compounds listedin Table 2 which fall within Formula III and IIIA, while Table 6similarly lists the corresponding values of the compounds listed inTable 2 which fall within Formulae XVIII and XVIIIA. Table 7 givesanalytical data for most of the compounds mentioned in Tables 2-6.

In the following Tables, compounds marked (c) after the compound No. are"control" compounds i.e. compounds similar to those of the invention butpossessing different values of the variable substituents. These controlcompounds are provided to show that the properties of the instantcompounds become less advantageous when the substituent values falloutside the ranges given.

                                      TABLE 2                                     __________________________________________________________________________    Compound                                                                      No.                                                                           __________________________________________________________________________    1(c)  [(2,3,7,8,10,16-hexamethyl-3,7,11,15,18,22-hexaazabicyclo[7.7.7]              tricosa-1,8,10,15,17,22-hexaene-κ.sup.4 N)nickel(II)]                   hexafluorophosphate                                                     2(c)  [acetonitrile(2,3,7,8,10,16-hexamethyl-3,7,11,15,18,22-hexaazabicycl          o                                                                             [7.7.7]tricosa-1,8,10,15,17,22-hexaene-κN)cobalt(II)]                   hexafluorophos-                                                               phate                                                                   3(c)  [chloro(2,3,7,8,10,16-hexamethyl-3,7,11,15,22-hexaazabicyclo[7.7.7]           tricosa-1,8,10,15,17,22-hexaene-κ.sup.4 N)iron(II)] hexafluoro          phosphate                                                               4     [2,9,11,17-tetramethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetra-            cosa-1,9,11,16,18,23-hexaene-κ.sup.4 N)nickel(II)] hexafluorop          hosphate                                                                5     [ch1oro(2,9,11,17-tetramethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]           5                                                                             tetracosa-1,9,11,16,18,23-hexaene-κ.sup.4 N(iron(II)]                   hexafluorophosphate                                                     6     [(2,3,8,9,11,17-hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetr          a-                                                                            cosa-1,9,11,16,18,23-hexaene-κ.sup.4 N)nickel(II)] hexafluorop          hosphate                                                                7     [(2,3,8,9,11,17-hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetr          a-                                                                            88 .sup.4 N)cobalt(II)] hexafluorophosphate                             8     [chloro(2,3,8,9,11,17-hexamethyl-3,8,12,16,19,23-hexaazabiclo[8.7.7]          tetracosa-1,9,11,16,18,23-hexaene-κ.sup.4 N)iron(II)]                   hexafluorophosphate                                                     9     [(11,17-dimethyl-2,9-diphenyl-3,8,12,16,19,23,-hexaazabicyclo[8.7.7]          tetracosa-1,9,11,16,18,23-hexaene-κ.sup.4 N)nickel(II)]                 hexafluorophosphate                                                     10    [acetonitrile(11,17-dimethyl-2,9-diphenyl,3,8,12,16,19,23-hexaazabic          yclo                                                                          [8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ.sup.4 N)cobalt(II)]           hexafluorophos-                                                              phate                                                                   11    [(3,8,11,17-tetramethyl-2-,9-diphenyl-3,8,12,16,19,23-hexaazabicyclo          [8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ.sup.4 N)nickel(II)]           hexafluoro-                                                                  phosphate                                                               12    [(3,8,11,17-tetramethyl-2,9-diphenyl-3,8,12,16,19,23-hexaazabicyclo           [8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ.sup.4 N)cobalt(II)]           hexafluoro-                                                                  phosphate                                                               13    [chloro(3,8,11,17-tetramethyl-2,9-diphenyl-3,8,12,16,19,23-hexaaza-           - bicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ.sup.4)iron          (II)]- hexafluorophosphate                                              14    [chloro(2,3,8,9,11,17-hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.          7]                                                                            tetracosa-1,9,11,16,18,23-hexaene-κ.sup.4 N)copper(II)]hexafIu          orophosphate                                                            15    [2,9-di- .sub.-t-butyl-11,17 dimethyl-3,8,12,16,19,23-hexaazabicyclo          [8.7.7]                                                                       tetracosa-1,9,11,16,18,23-hexaene-κ.sup.4 N)nickel(II)]                 hexafluorophosphate                                                     16    [(2,10,12,18-tetramethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentac          osa-                                                                          1,10,12,17,19,24-hexaene-κ.sup.4 N)nickel(II)] hexafluorophosp          hate                                                                    17    [(2,10,12,18-tetramethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentac          osa-                                                                          1,10,12,17,19,24-hexaene-κ.sup.4 N)cobalt(II)]hexafluorophosph          ate                                                                     18    [chloro(2,10,12,18-tetramethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]          pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)iron(II)]                  chloride                                                                19    trans-[(carbonyl)(pyridine)(2,10,12,18-tetramethyl-3,9,13,17,20,24-           hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ.sup.          4 N)iron(II)]                                                                 hexafluorophosphate                                                     20    [(2,3,9,10,12,18-hexamethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]             pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)nickel(II)]                hexafluorophosphate                                                     21    [(2,3,9,10,12,18-hexamethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]             pentacosa-l,10,12,17,19,24-hexaene-κ.sup.4 N)cobalt(II)]                hexafluorophosphate                                                     22    [chloro(2,3,9,10,12,18-hexamethyl-3,9,13,17,20,24-hexaazabicyclo[9.7          .7]                                                                           pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)iron(II)]                  hexafluorophosphate                                                     23    trans-[bis-thiocyanato(2,3,9,10,12,18-hexamethyl-3,9,13,17,20,24-             hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ.sup.          4 N)cobalt                                                                    (III)]hexafluorophosphate                                               24    [(12,18-dimethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicyclo[                9.7.7]                                                                        pentacosa-1,10,12,17,19,24-hexane-κ.sup.4 N)nickel(II)]hexaflu          orophosphate                                                            25    [(12,18-dimethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]          pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)cobalt(II)]                hexafluorophosphate                                                     26    [(3,9,12,18-tetramethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicyclo          [9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)nickel(II)          ] hexafluoro-                                                                 phosphate                                                               27    [(3,9,12,18-tetramethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicyclo          [9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)cobalt(II)          ] hexafluoro-                                                                 phosphate                                                               28    [chloro(3,9,12,18-tetramethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazab          icyclo                                                                        [9.7.7]pentacosa-1,10,12,17,19,24-hexane-κ.sup.4 N)iron(II)]            hexafluorophosphate                                                     29    [(2,10-di- .sub.-t-butyl-12,18-dimethyl-3,9,13,17,20,24-hexaazabicyc          lo[9.7.7]                                                                     pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)nickel(II)]                hexafluorophosphate                                                     30    [acetonitrile(2,10-di- .sub.-t-butyl-12,18-dimethyl-3,9,13,17,20,24-          hexaaza-                                                                      bicyclo[9.7.7]pentacosa-1,10,12,17,24-hexaene-κ.sup.4                   N)cobalt(II)]- hexafluorophosphate                                      31    [(2,11,13,19-tetramethy1-3,10,14,18,21,25-hexaazabicyclo[10.7.7]              hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)]                 hexafluorophosphate                                                     32    [(2,11,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]              hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)cobalt(II)]                 hexafluorophosphate                                                     33    [chloro(2,11,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.          7]                                                                            hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)iron(II)]                   hexafluorophosphate                                                     34     ----trans-[(carbonyl)(pyridine)(2,11,13,19-tetramethyl-3,10,14,18,2          1,25-                                                                         hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.          4 N)iron(II)]                                                                 hexafluorophosphate                                                     35    [ethanol(2,11,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7          .7]                                                                           hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)copper(II)]                 hexafluorophosphate                                                     36    [(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]          hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)]hexaflu          orophosphate                                                            37    [(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]          hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)]chlorid          e                                                                       38    [(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]          hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)cobalt(II)]hexaflu          orophosphate                                                            39    [1-methylimidazole(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaa          za-                                                                           bicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4                N)cobalt(II)]                                                                 hexafluorophosphate                                                     40    [imidazole(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicycl          o-                                                                            [10.7.7]hexacosa-1,11,13,18,20,25-κ.sup.4 N)cobalt(II)]                 hexafluoro-                                                                   phosphate                                                               41    [pyridine(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo          -                                                                             [10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)cobalt(II)          ] hexafluoro- - phosphate                                               42    [thiocyanato(2,3,10,11,13,19-hexamethyl-3,10,14,18,25-hexaazabicyclo          -                                                                             [10.7.7]hexacosa-1,11,13,20,25-hexaene-κ.sup.4 N)cobalt(II)]            hexafluoro-                                                                   phosphate                                                               43    trans-[bis-thiocyanato(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-           hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.          4 N)cobalt                                                                    (III)] hexafluorophosphate                                              44    trans[bis-cyanato(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-                hexaazabicyclo]10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.          4 N)cobalt                                                                    (III)] hexafluorophosphate                                              44    trans-[bis-cyanato(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-               hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.          4 N)cobalt                                                                    (III)] hexafluorophosphate                                              45    trans-[bis-azido(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaaza          -                                                                             bicyclo[10.7.7] hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4               N)cobalt(III)]                                                                hexafluorophosphate                                                     46    [chloro(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo-           [10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)iron(II)]           hexafluoro-                                                                   phosphate                                                               47    trans-[(carbonyl)(acetonitrile)(2,3,10,11,13,19-hexamethyl-3,10,14,1          8,21,25-                                                                      hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.          4 N)iron(II)]                                                                 hexafluorophosphate                                                     48    trans-[(carbonyl)(pyridine)(2,3,10,11,13,19-hexamethyl-3,10,14,18,21          ,25-                                                                          hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.          4 N)iron(II)]                                                                 hexafluorophosphate                                                     49    trans-[(carbonyl)(1-methylimidazole)(2,3,10,11,13,19-hexamethyl-3,10          ,                                                                             14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-          κ.sup.4 N)iron(II)] hexafluorophosphate                           50    [chloro(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[1          0.7.7]                                                                        hexacosa-1,11,13,18,20,15-hexaene-κ.sup.4 N)iron(III)]                  hexafluorophosphate                                                     51    [chloro(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[1          0.7.7]                                                                        hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)manganese(II)]              hexafluorophosphate                                                     52    [chloro(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[1          0.7.7]                                                                        hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)manganese(III)]             hexafluorophosphate                                                     53    [(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]          hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)copper(II)]                 hexafluorophosphate                                                     54    [13,19,dimethyl-2,11-diphenyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7          ]                                                                             hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)]                 hexafluorophosphate                                                     55    [13,19-dimethyl-2,11,diphenyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7          ]                                                                             hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)cobalt(II)]                 hexafluorophosphate                                                     56    [(3,10,13,19-tetramethyl-2,11-diphenyl-3,10,14,18,21,25-hexaazabicyc          lo                                                                            [10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ .sup.4                      N)nickel(II)] hexafluoro-                                                     phosphate                                                               57    [(3,10,13,19-tetramethyl-2,11-diphenyl-3,10,14,18,21,25-hexaazabicyc          lo                                                                            [10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)cobalt(II)          ] hexafluoro-                                                                 phosphate                                                               58    [chloro(3,10,13,19-tetramethyl-2,11-diphenyl-3,10,14,18,21,25-hexaaz          a-                                                                            bicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4                N)iron(II)]                                                                   hexafluorophosphate                                                     59    [chloro(3,10-dibenzyl-13,19-dimethyl-2,11-diphenyl-3,10,14,18,21,25-          hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.          4 N)iron(II)]                                                                 hexafluorophosphate                                                     60    [(2,11-di- .sub.-t-butyl-13,19-dimethyl-3,10,14,18,21,25-hexaazabicy          clo[10.7.7]                                                                   hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)]                 hexafluorophosphate                                                     61    [(2,11-di- .sub.-t-butyl-13,19-dimethyl-3,10,14,18,21,25-hexaazabicy          clo[10.7.7]                                                                   hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)cobalt(II)]                 hexafluorophosphate                                                     62    [(2,11,-di- -n-heptyl-13,19-dimethyl-3,10,14,18,21,25-hexaazabicyclo          [10.7.7]                                                                      hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)]                 hexafluorophosphate                                                     63    [(3,10,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexa          cosa-                                                                         1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)] hexafluorophosp          hate                                                                    64    [acetonitrile(3,10,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo          [10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)cobalt(II)          ] hexafluoro-                                                                 phosphate                                                               65(c) [(13,19-dimethyl-3,10,14,18,21,25-hexaazatricyclo[10.7.7.6.sup.2,11           ]dotriaconta-                                                                 1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)] hexafluorophosp          hate                                                                    66    [(13,19-dimethyl-3,10,14,18,21,25-hexaazatricyclo[10.7.7.7.sup.2,11           ]tri-                                                                         triaconta-1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)]                hexafluorophosphate                                                     67    [(13,19-dimethyl-3,10,14,18,21,25-hexaazatricyclo[10.8.sup.2,11.7.7]          tetra-                                                                        triaconta-1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)]                Hexafluoro-                                                                   phosphate                                                               68    [(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazabicyclo)11.7.7]-             heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)nickel(II)]                hexafluoro-                                                                   phosphate                                                               69    [acetonitrile(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazabicyclo          7                                                                             [11.7.7]heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)cobalt(II          )] hexafluoro-                                                                phosphate                                                               70    [(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazabicyclo[11.7.7]          heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)nickel(II)]                hexafluoro-                                                                   phosphate                                                               71    [(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazabicyclo[11.7.7]          heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)cobalt(II)]                hexafluoro                                                                    phosphate                                                               72    [bis-thiocyanato(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaaza          -                                                                             bicyclo[11.7.7]heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4               N)cobalt(III)]                                                                hexafluorophosphate                                                     73    [(14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazabicyclo[11.7.          7]                                                                            heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)nickel(II)]                hexafluoro                                                                    phosphate                                                               74    [(14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazabicyclo[11.7.          7]                                                                            heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)cobalt(II)]                hexafluoro                                                                    phosphate                                                               75    [(3,11,14,20-tetramethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazabicyc          lo-                                                                           [11.7.7]heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)nickel(II          )] hexafluoro-                                                                phosphate                                                               76    [(3,11,14,20-tetramethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazabicyc          lo-                                                                           [11.7.7]heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)cobalt(II          )] hexafluoro-                                                                phosphate                                                               77    [(2,12-di- .sub.-t-butyl-14,20-dimethyl-3,11,15,19,22,26-hexaazabicy          clo[11.7.7]                                                                   heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)nickel(II)]                hexafluoro                                                                    phosphate                                                               78    [(2,12-di- .sub.-t-butyl-14,20-dimethyl-3,11,15,19,22,26-hexaazabicy          clo[  11.7.7]                                                                 heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)cobalt(II)]                hexafluoro                                                                    phosphate                                                               79    [(14,20-dimethyl-3,11,15,19,22,26-hexaazatricyclo[11.8.sup.2,12               .7.7]penta-                                                                   triaconta-1,12,14,19,21,26-hexaene-κ.sup.4 N)nickel(II)]                hexafluorophosphate                                                     80    [(2,13,15,21-tetramethyl-3,12,16,20,23,27-hexaazabicyclo[12.7.7]octa          cosa-                                                                         1,13,15,20,22,27-hexaene-κ.sup.4 N)nickel(II)] hexafluorophosp          hate                                                                    81    [(2,13,15,21-tetramethyl-3,12,16,20,23,27-hexaazabicyclo[12.7.7]octa          cosa-                                                                         1,13,15,20,22,27-hexaene-κ.sup.4 N)cobalt(II)] hexafluorophosp          hate                                                                    82    [(2,3,12,13,15,21-hexamethyl-3,12,16,20,23,27-hexaazabicyclo[12.7.7]          N                                                                             octacosa-1,13,15,20,22,17-hexaene-κ.sup.4 N)nickel(II)]                 hexafluorophosphate                                                     83    [acetonitrile(2,3,12,13,15,21-hexamethyl-3,12,16,20,23,27-hexaazabic          yclo-                                                                         [12.7.7] octacosa-1,13,15,20,22,27-hexaene-κ.sup.4 N)cobalt(II          )] hexafluoro                                                                 phosphate                                                               84    [(15,21-dimethyl-2,13-diphenyl-3,12,16,20,23,27-hexaazabicyclo-[12.7          .7]                                                                           octacosa-1,13,15,20,22,27-hexane-κ-.sup.4 N)nickel(II)]                 hexafluoro                                                                    phosphate                                                               85    [acetonitrile(3,12,15,21-tetramethyl-2,13-diphenyl-3,12,16,20,23,27-          hexaazabicyclo[12.7.7]octacosa-1,13,15,20,22,27-hexane-κ.sup.4           N)cobalt(II)]                                                                hexafluorophosphate                                                     86    [(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1.s          up.5,9 ]                                                                      octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ.sup.4 N)nickel(I          I)] hexafluoro-                                                               phosphate                                                               87    [acetonitrile(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricycl          o-                                                                            [11.7.7.1.sup.5,9 ] octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kap          pa..sup.4 N)cobalt(II)]                                                       hexafluorophosphate                                                     88    [chloro(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7          .7.1.sup.5,9 ]                                                                octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ.sup.4 N)iron(II)          ] hexafluoro-                                                                 phosphate                                                               89    trans-[(carbonyl)(pyridine)(2,12,14,20-tetramethyl-3,11,15,19,22,26-          hexaazatricyclo[11.7.7.1.sup.5,9 ] octacosa-1,5,7,9(28),12,14,19,21,          26-nonaene-                                                                   κ.sup.4 N)iron(II)] hexafluorophosphate                           90    trans-[(carbonyl)(1-methylimidazole)(2,12,14,20-tetramethyl-3,11,15,          19,                                                                           22,26-hexaazatricyclo[11.7.7.1.sup.5,9 ] octacosa-1,5,7,9(28),12,14,          19,21,26-                                                                     nonaene-κ.sup.4 N)iron(II)] hexafluorophosphate                   91    trans-[(carbonyl)(imidazole)(2,12,14,20-tetramethyl-3,11,15,19,22,26          -                                                                             hexaazatricyclo[11.7.7.1.sup.5,9 ] octacosa-1,5,7,9(28),12,14,19,21,          26-nonaene-                                                                   κ.sup.4 N)iron(II)] hexafluorophosphate                           92    trans-[(carbonyl)(4-aminopyridine)(2,12,14,20-tetramethyl-3,11,15,19          ,22,26-                                                                       hexaazatricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,2          6-nonaene-                                                                    κ.sup.4 N)iron(II)] hexafluorophosphate                           93    [(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo-[11.7.          7.1.sup.5,9 ]                                                                 octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ.sup.4 N)nickel(I          I)] hexafluoro-                                                               phosphate                                                               94    [aquo(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo-            [11.7.7.1.sup.5,9 ] octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kap          pa..sup.4 N)cobalt(II)]                                                       hexafluorophosphate                                                     95    [chloro(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo-          [11.7.7.1.sup.5,9 ] octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kap          pa..sup.4 N(iron(II)]                                                         hexafluorophosphate                                                     96    trans-[(carbonyl)(1-methylimidazole)(2,3,11,12,14,20-hexamethyl-              3,11,15,19,22,26-hexaazatricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(          28),                                                                          12,14,19,21,26-nonaene-κ.sup.4 N)iron(II)] hexafluorophosphate    97    trans-[(carbonyl)(acetonitrile)(2,3,11,12,14,20-hexamethyl-3,11,15,1          9,                                                                            22,26-hexaazatricyclo[11.7.7.1.sup.5,9 ] octacosa-1,5,7,9(28),12,14,          19,21,26-                                                                     nonaene-κ.sup.4 N)iron(II)]hexafluorophosphate                    98    trans-[(carbonyl)(imidazole)(2,3,11,12,14,20-hexamethyl-3,11,15,19            22,26-hexaazatricyclo[11.7.7.1.sup.5,9 ] octacosa-1,5,7,9(28),12,14,          19,21,26-                                                                     nonaene-κ.sup.4 N)iron(II)] hexafluorophosphate                   99    trans-[(carbonyl)(4-aminopyridine)(2,3,11,12,14,20-hexamethyl-3,11,1          5,19                                                                          22,26-hexaazatricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,1          9,21,26-                                                                      nonaene-κ.sup.4 N)iron(II)] hexafluorophosphate                   100   [chloro(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo-          [11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kapp          a..sup.4 N)iron(II)]                                                          hexafluorophosphate                                                     101   [(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7          .1.sup.5,9 ]                                                                  octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ.sup.4 N)manganes          e(II)] hexafluoro-                                                            phosphate                                                               102   [chloro(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo-          S                                                                             [11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kapp          a..sup.4 N)manganese                                                          (II)] hexafluorophosphate                                               103   [acetonitrile(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatri          cyclo-                                                                        [11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kapp          a..sup.4 N)copper(II)]                                                        hexafluorophosphate                                                     104   [(3,11-di- -n-butyl-2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazat          ricyclo-                                                                      [11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kapp          a..sup.4 N)nickel(II)]                                                        hexafluorophosphate                                                     105   [(2,12,14,20-tetramethyl-3,11-di-propylnitrile-3,11,15,19,22,26-hexa          aza-                                                                          tricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonae          ne-κ.sup.4 N)                                                           nickel(II)] hexafluorophosphate                                         106   [(3,11-dibenzyl-2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricy          clo                                                                           [11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kapp          a..sup.4 N)nickel                                                             (II)] hexafluorophosphate                                               107   [acetonitrile(3,11-dibenzyl-2,12,14,20-tetramethyl-3,11,15,19,22,26-          hexaazatricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(280,12,14,19,21,2          6-                                                                            nonaene-κ.sup.4 N)iron(II)] hexafluorophosphate                   108   [3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[                     11.7.7.1.sup.5,9 ]                                                            octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ.sup.4 N)nickel(I          I)] hexafluoro-                                                               phosphate                                                               109   [(2,12-di- -n-heptyl-14,20-dimethyl-3,11,15,19,22,26-hexaazatricyclo          -                                                                             [11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kapp          a..sup.4 N)nickel(II)]                                                        hexafluorophosphate                                                     110   [(2,12-di- -n-heptyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaaza          0                                                                             tricyclo-[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nona          ene-κ.sup.4 N)                                                          nickel(II)] hexafluorophosphate                                         111   [chloro(2,12-di- -n-heptyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-h          exaaza-                                                                       tricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonae          ne-κ.sup.4 N)                                                           iron(II)] hexafluorophosphate                                           112   [(14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo-              [11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kapp          a..sup.4 N)nickel                                                             (II)] hexafluorophosphate                                               113   [acetonitrile(14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaaza-          tricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonae          ne-κ.sup.4 N)                                                           cobalt(II)] hexafluorophosphate                                         114   [(3,11,14,20-tetramethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricy          clo-                                                                          [11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kapp          a..sup.4 N)nickel(II)]                                                        hexafluorophosphate                                                     115   [(3,11,14,20-tetramethyl-2,12,-diphenyl-3,11,15,19,22,26-hexaazatric          yclo-                                                                         [11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kapp          a..sup.4 N)cobalt(II)]                                                        hexafluorophosphate                                                     116   [acetonitrile(3,11,14,20-tetramethyl-2,12-diphenyl-3,11,15,19,22,26-          N                                                                             hexaazatricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,2          6-                                                                            nonaene-κ.sup.4 N)iron(II)] hexafluorophosphate                   117   [(3,11-dibenzyl-14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaaz          a-                                                                            tricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonae          ne-κ .sup.4 N)                                                          nickel(II)] hexafluorophosphate                                         118   [acetonitrile(3,11-dibenzyl-14,20-dimethyl-2,12-diphenyl-3,11,15,19,          N                                                                             22,26-hexaazatricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,1          9,21,26-                                                                      nonaene-κ.sup.4 N)iron(II)] hexafluorophosphate                   119   [chloro(2,12-di-p-methoxyphenyl-3,11,14,20-tetramethyl-3,11,15,19,22          ,26-                                                                          hexaazatricyclo-[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,          26-nonaene-                                                                   κ.sup.4 N)iron(II)] hexafluorophosphate                           120   [chloro(2,12-di-p-chlorophenyl-3,11,14,20-tetramethyl-3,11,15,19,22,          26-                                                                           hexaazatricyclo-[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,          26-nonaene-                                                                   κ.sup.4 N)iron(II)] hexafluorophosphate                           121   [chloro(2,12-di-p-fluorophenyl-3,11,14,20-tetramethyl-3,11,15,19,22,          26-                                                                           hexaazatricyclo-[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,          26-nonaene-                                                                   κ.sup.4 N)iron(II)] hexafluorophosphate                           122   [chloro(2,12-di(3,5-dimethoxyphenyl)-3,11,14,20-tetramethyl-3,11,15,          19,                                                                           22,26-hexaazatricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,1          9,21,26-                                                                      nonaene-κ.sup.4 N)iron(II)] hexafluorophosphate                   123   [(14,20-dimethyl-3,11,15,19,22,26-hexaazatetracyclo[11.8.sup.2,12.7.          7.1.sup.5,9 ]                                                                 hexatriaconta-1,5,7,9(36),12,14,19,21,26-nonaene-κ.sup.4                N)nickel(II)]                                                                 hexafluorophosphate                                                     124   [(14,20-dimethyl-3,11,15,19,22,26-hexaazatetracyclo[11.7.7.7.sup.2,1          2.1.sup.5,9 ]                                                                 pentatriaconta-1,5,7,9(35),12,14,19,21,26-nonaene-κ.sup.4               N)nickel(II)]                                                                 hexafluorophosphate                                                     125   [(2,11,13,19-tetramethyl-3,10,14,18,21,25-hexazatricyclo[10.7.7.2.su          p.5,8 ]                                                                       octacosa-1,5,7,11,13,18,20,25,27-nonaene-κ.sup.4 N)nickel(II)]           hexafluoro-                                                                  phosphate                                                               126   [chloro(2,11,13,19-tetramethyl-3,10,14,18,21,25-hexaazatricyclo[10.7          .7.2.sup.5,8 ]                                                                octacosa-1,5,7,11,13,18,20,25,27-nonaene-κ.sup.4 N)iron(II)]            hexafluoro                                                                    phosphate                                                               127   trans-[(carbonyl)(aectonitrile)(2,11,13,19-tetramethyl-3,10,14,18,21          ,25-                                                                          hexaazatricyclo[10.7.7.2.sup.5,8 ]octacosa-1,5,7,11,13,18,20,25,27-n          onaene-                                                                       κ.sup.4 N)iron(II)] hexafluorophosphate                           128   trans-[(carbonyl)(pyridine)(2,11,13,19-tetramethyl-3,10,14,18,21,25-          ,                                                                             hexaazatricyclo[10.7.7.2.sup.5,8 ]octacosa-1,5,7,11,13,18,20,25,27-n          onaene-                                                                       κ.sup.4 N)iron(II)] hexafluorophosphate                           129   trans-[(carbonyl)(1-methylimidazole)(2,11,13,19-tetramethyl-3,10,14,          18,                                                                           21,25-hexaazatricyclo[10.7.7.2.sup.5,8 ]octacosa-1,5,7,11,13,18,20,2          5,27-                                                                         nonaene-κ.sup.4 N)iron(II)] hexafluorophosphate                   130   [(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazatricyclo[10.7.7          .2.sup.5,8 ]                                                                  octacosa-1,5,7,11,13,18,20,25,27-nonaene-κ.sup.4 N)nickel(II)]           hexafluoro                                                                   phosphate                                                               131   [2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazapentacyclo[11.7.7.4.          sup.7,7                                                                       .4.sup.28,29.4.sup.30,31 ] nonatriconta-1,12,14,19,21,26,28(20),30(3          1),32,34,36,38-                                                               dodecaene-κ.sup.4 N)nickel(II)] hexafluorophosphate               132   [chloro(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazapentacyclo[11          .7.7                                                                          .4.sup.7,7.4.sup.28,29.4.sup.30,31 ] nonatriconta-1,12,14,19,21,28(2          9),30(31),32,34,36,                                                           38-dodecaene-κ.sup.4 N)iron(II)] chloride                         133   trans-[(carbonyl)(pyridine)(2,12,14,20-tetramethyl-3,11,15,19,22,26-          a                                                                             hexaazapentacyclo[11.7.7.4.sup.7,7.4.sup.28,29.4.sup.30,31 ]                  nonatriconta-1,12,14,19,21,                                                   26,28(29),30(31),32,34,36,38-dodecaene-κ.sup.4 N)iron(II)]              hexafluoro                                                                    phosphate                                                               134   trans-[(carbonyl)(1-methylimidazole)(2,12,14,20-tetramethyl-3,11,15,          19,                                                                           22,26-hexaazapentacyclo[11.7.7.4.sup.7,7.4.sup.28,29.4.sup.30,31 ]            nonatriconta-                                                                 1,12,14,19,21,26,28(29),30(31),32,34,36,38-dodecaene-κ.sup.4            N)iron(II)]                                                                   hexafluorophosphate                                                     135   [(4-methoxycarbonyl-2,10,12,18-tetramethyl-3,9,13,17,20,24-hexaaza-           0                                                                             bicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4                N)nickel(II)]                                                                 hexafluorophosphate                                                     136   [2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1.su          p.5,9 ]                                                                       octacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)nickel(II)]hexaflu          orophosphate                                                            137   [(3,6,6,9,12,18-hexamethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicy          clo-                                                                          [9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)nickel(II)          ] hexafluoro                                                                  phosphate                                                               138   [(7-methoxy-2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricy          clo-                                                                          [11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kapp          a..sup.4 N)nickel(II)]                                                        hexafluorophosphate                                                     139   [(2,10,12,18-tetramethyl-6-thia-3,9,13,17,20,24-hexaazabicyclo[9.7.7          ]                                                                             pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)nickel(II)]                hexafluoro                                                                    phosphate                                                               140   [(2,11,13,19-tetramethyl-6-thia-3,10,14,18,21,25-hexaazabicyclo[10.7          .7]                                                                           hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)]                 hexafluoro-                                                                   phosphate                                                               141   [(7-methoxycarbonyl-2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-              hexaazatricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,2          6-                                                                            nonaene-κ.sup.4 N)nickel(II)] hexafluorophosphate                 142   [(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26,28-heptaazatricyclo             [11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-.kapp          a..sup.4 N)nickel                                                             (II)] hexafluorophosphate                                               143   [(2,12,14,20-tetramethyl-3,7,11,15,19,22,26-heptaazabicyclo[11.7.7]           r                                                                             heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)nickel(II)]                hexafluoro                                                                    phosphate                                                               144   [(2,7,12,14,20-pentamethyl-3,7,11,15,19,22,26-heptaazabicyclo[11.7.7          ]                                                                             heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)nickel(II)]                hexafluoro                                                                    phosphate                                                               145   [(2,7,12,14,20-pentamethyl-3,7,11,15,19,22,26-heptaazabicyclo[11.7.7          ]                                                                             heptacosa-1,12,14,19,21,26-hexaene-κ.sup.4 N)cobalt(II)]                hexafluoro                                                                    phosphate                                                               146(c)                                                                              [(2,8,-bis-dimethylamino-10,16-dimethyl-11,15,18,22-tetrabicyclo-             [7.7.7]tricosa-1,8,10,17,22-hexaene-κ  .sup.4 N)nickel(II)]             hexafluoro                                                                    phosphate                                                               147(c)                                                                              [acetonitrile(2,8-bis-dimethylamino-10,16-dimethyl-11,15,18,22-tetra          aza-                                                                          bicyclo[7.7.7]tricosa-1,8,10,15,17,22-hexaene-κ.sup.4                   N)cobalt(II)] hexafluoro-                                                     phosphate                                                               148(c)                                                                              [(11,17-dimethyl-2,9-bis-methylamino-12,16,19,23-tetraazabicyclo[8.7          .7]                                                                           tetracosa-1,9,11,16,18,23-hexaene-κ.sup.4 N)(II)] hexafluoroph          osphate                                                                 149(c)                                                                              [(2,9-bis(dimethylamino)-11,17-dimethyl-12,16,19,23-tetraaza-                 bicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ.sup.4                 N)nickel(II)] hexafluoro-                                                     phosphate                                                               150(c)                                                                              [acetonitrile(2,9-bis(dimethylamino)-11,17-dimethyl-12,16,19,23-tetr          aaza-                                                                         bicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ.sup.4                 N)cobalt(II)] hexafluoro-                                                     phosphate                                                               151   [(12,18-dimethy-2,10-bis-methylamino-13,17,20,24-tetraazabicyclo[9.7          .7]                                                                           pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)nickel(II)]                hexafluoro                                                                    phosphate                                                               152   [(12,18-dimethyl-2,10-bis-methylamino-13,17,20,24-tetraazabicyclo[9.          7.7]                                                                          pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)cobalt(II)]                hexafluoro                                                                    phosphate                                                               153   [chloro(12,18-dimethyl-2,10-bis-methylamino-13,17,20,24-tetraazabicy          clo-                                                                          [9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)iron(II)]           hexafluoro                                                                    phosphate                                                               154   [(12,18-dimethyl-2,10-bis-propylamino-13,17,20,24-tetraazabicyclo[9.          7.7]                                                                          pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)nickel(II)]                hexafluoro                                                                    phosphate                                                               155   [acetonitril(12,18-dimethyl-2,10-bis-propylamino-13,17,20,24-tetraaz          a-                                                                            bicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4                N)cobalt(II)]                                                                 hexafluorophosphate                                                     156   [(2,10-bis-benzylamino-12,18-dimethyl-13,17,20,24-tetrabicyclo-               [9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)(II)]               hexafluoro-                                                                   phosphate                                                               157   [(2,10-bis-dimethylamino-12,18-dimethyl-12,17,20,24-tetraazabicyclo-          J                                                                             [9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ                             .sup.4 N)nickel(II)] hexafluoro-                                              phosphate                                                               158   [aquo(2,10-bis-dimethalamino-12,18-dimethyl-12,17,20,24-tetraazabicy          clo-                                                                          [9.9.7]pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)cobalt(II)          ] hexafluoro-                                                                 phosphate                                                               159   [chloro(2,10-bis-dimethylamino-12,18-dimethyl-13,17,20,24-tetraazabi          cyclo-                                                                        [9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ.sup.4 N)iron(II)]           hexafluoro                                                                    phosphate                                                               160   [(13,19-dimethyl-2,11-bis-methylamino-14,18,21,25-tetraazabicyclo[10          .7.7]-                                                                        hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)]                 hexafluorophosphate                                                     161   [(2,11-bis-dimethylamino-13,19-dimethyl-14,18,21,25-tetraazabicyclo[          10.7.7]-                                                                      hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4 N)nickel(II)]                 hexafluorophosphate                                                     162   [acetonitrile(2,11-bis-dimethylamino-13,19-dimethyl-14,18,21,25-              tetraazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup          .4 N)cobalt(II)]                                                              hexafluorophosphate                                                     163   [chloro(2,11-bis-dimethylamino-13,19-dimethyl-14,18,21,25-tetraaza-           u                                                                             bicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4                N)iron(II)] hexafluoro-                                                       phosphate                                                               164   [(2,2,9,10,12,18-hexamethyl-22-(1-methyl-2-pyridinio)-3,9,13,17,20,2          4-                                                                            hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ.sup.          4 N)nickel(II)]                                                               hexafluorophosphate                                                     165   [(2,3,10,11,13,19-hexamethyl-23-(1-methyl-2-pyridinio)-3,10,14,18,21          ,25-                                                                          hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.          4 N)nickel(II)]                                                               hexafluorophosphate                                                     166   [(2,3,10,11,13,19-hexamethyl-23-(1-methyl-2-pyridinio)-3,10,14,18,21          ,25-                                                                          hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-κ.sup.4                 N)cobalt(II)]                                                                 hexafluorophosphate                                                     167   [(2,2,11,12,14,20-hexamethyl-24-(1-methyl-2-pyridinio)-3,11,15,19,22          ,26-                                                                          hexaazatricyclo[11.7.7.1.sup.5,9 ]octacosa-1,5,7,9(28),12,14,19,21,1          6-nonaene-                                                                    κ.sup.4 N)nickel(II)] hexafluorophosphate                         168   [(2,3,10,11,13,19-hexamethyl-23-(2-pyridyl)-3,10,14,18,21,25-hexaaza          -                                                                             bicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ.sup.4                N)cobalt(II)]-                                                                hexafluorophosphate                                                     169   [(2,3,10,11,12,19-hexamethyl-3,10,14,18,21,24-hexaazabicyclo[10.7.6]          pentacosa                                                                     1,11,13,18,20,24-hexaene-κ.sup.4 N)nickel(II)] hexafluorophosp          hate                                                                    170   [(2,3,8,9,11,17-hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetr          acosa-                                                                        1.9,11,16,18,23-hexaene-κ.sup.4 N)] hexafluorophosphate           171   [chloro(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7          .7.1.sup.5,9 ]                                                                octocosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ.sup.4 N)iron(II)          ] chloride dimeth-                                                            anolate                                                                 172   [(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazapentacyclo[11.7.7.4          .sup.7,7.4.sup.28,                                                            .sup.29.4.sup.30,31 ]nonatriaconta-1,12,14,19,21,26,28(29),30(31),32          ,34,36,38-dode-                                                               caene-κ.sup.4 N)zinc(II)]chloride                                 173   [(2,18,20,26-tetramethyl-3,6,14,17,21,25,28,32-octaazapentacyclo-             [17.7.7.2.sup.3,6.2.sup.14,17.1.sup.8,12 ]octatriaconta-1,8,12,12(38          ),18,20,25,27,                                                                32-nonaene-κ.sup.4 N)nickel(II)] hexafluorophosphate              174   [(2,18,20,26-tetramethyl-3,6,14,17,21,25,28,32-octaazapentacyclo-             [17.7.7.2.sup.3,6.2.sup.14,17.1.sup.8,12 ]octatriconta-1,8,10,12(38)          ,18,20,25,                                                                    27,32-nonaene-κ.sup.4 N)nickel(II) chloride                       175   [methanol(2,18,20,26-tetramethyl-3,6,14,17,21,25,28,32-octaazapentac          yclo-                                                                         [17.7.7.2.sup.3,6.2.sup.14,17.1.sup.8,12 ]octatriaconta-1,8,10,12(38          ),18,20,25,27,32-                                                             nonaene-κ.sup.4 N)cobalt(II)] hexafluorophosphate                 176   [(2,17,19,25-tetramethyl-3,6,13,16,20,24,27,31-octaazapentacyclo-             [16.7.7.2.sup.8,11.2.sup.3,6.2.sup.13,16 ]octatriaconta-1,8,10,17,19          ,24,26,31,33-                                                                 nonaene-κ.sup.4 N)nickel(II)] hexafluorophosphate                 177   [(2,17,19,25-tetramethyl-3,6,13,16,20,24,27,31-octaazapentacyclo-             [16.7.7.2.sup.8,11.2.sup.3,6.2.sup.13,16 ]octatriaconta-1,8,10,17,19          ,24,26,31,33-                                                                 nonaene-κ.sup.4 N)cobalt(II)]   hexafluorophosphate               178   [(2,9,10,17,19,25,33,34-octamethyl-3,6,13,16,20,24,27,31-octaazapent          acyclo-                                                                       [16.7.7.2.sup.8,11.2.sup.3,6.2.sup.13,16 ]octatriaconta-1,8,10,17,19          ,24,26,31,33-nonaene-                                                         κ.sup.4 N)nickel(II)] hexafluorophosphate                         179   [(2,9,10,17,19,25,33,34-octamethyl-3,6,13,16,20,24,27,31-octaazapent          acyclo-                                                                       [16.7.7.2.sup.8,11.2.sup.3,6.2.sup.13,16 ]octatriaconta-1,8,10,17,19          ,24,26,31,33-nonaene-                                                         κ.sup.4 N)nickel(II)] chloride                                    180   [(2,9,10,17,19,25,33,34-octamethyl-3,6,13,16,20,24,27,31-octaazapent          acyclo-                                                                       [16.7.7.2.sup.8,11.2.sup.3,6.2.sup.13,16 ]octatriaconta-1,8,10,17,19          ,24,26,31,33-nonaene-                                                         κ.sup.4 N)cobalt(II)] hexafluorophosphate                         181   [chloro(2,9,10,17,19,25,33,34-octamethyl-3,6,13,16,20,24,27,31-octaa          zapenta-                                                                      cyclo[16.7.7.2.sup.8,11.2.sup.3,6.2.sup.13,16 ]octatriaconta-1,8,10,          17,19,24,26,31,33-                                                            nonaene-κ.sup.4 N)iron(II)] hexafluorophosphate                   182   [aquo(2,9,10,17,19,25,33,34-octamethyl-3,6,13,16,20,24,27,31-octaaza          penta-                                                                        cylco[16.7.7.2.sup.8,11.2.sup.3,6.2.sup.13,16 ]octatriaconta-1,8,10,          17,19,24,26,31,33-                                                            nonaene-κ.sup.4 N)iron(II)] hexafluorophosphate                   183   [(2,9,10,17,19,25,33,34-octamethyl-3,6,13,16,20,24,27,31-octaazapent          acyclo-                                                                       [16.7.7.2.sup.8,11.2.sup.3,6.2.sup.13,16 ]octatriaconta-1,8,10,17,19          ,24,26,31,33-nonaene-                                                         κ.sup.4 N)copper(II)] hexafluorophosphate                         184   [(9,10,19,25,33,34-hexamethyl-2,17-diphenyl-3,6,13,16,20,24,27,31-oc          taaza-                                                                        pentacyclo-[16.7.7.2.sup.8,11.2.sup.3,6.2.sup.13,16 ]octatriaconta-1          ,8,10,17,19,24,26,31,33-                                                      nonaene-κ.sup.4 N)nickel(II)] hexafluorophosphate                 185   [(2,21,23,29-tetramethyl-3,6,17,20,24,28,31,35-octaazaheptacyclo-             [20.7.7.6.sup.8,15.2.sup.3,6.2.sup.17,20.0.sup.9,14.0.sup.37,42               ]hexatetraconta-1,8(37),9,11,13                                               15(42),21,23,28,30,35,38,40-tridecaene-κ.sup.4 N)nickel(II)]            hexafluoro                                                                    phosphate                                                               186   [(2,21,23,29-tetramethyl-3,6,17,20,24,28,31,35-octaazaheptacyclo-             [20.7.7.6.sup.8,15.2.sup.3,6.2.sup.17,20.0.sup.9,14.0.sup.37,42               ]hexatetraconta-1,8(37),9,11,13,                                              15(42),21,23,28,30,35,38,40-tridecaene-κ.sup.4 N)nickel(II)]            chloride                                                                187   [methanol(2,21,23,29-tetramethyl-3,6,17,20,24,28,31,35-octaazaheptac          yclo-                                                                         [20.7.7.6.sup.8,15.2.sup.3,6.2.sup.17,20.0.sup.9,14.0.sup.37,42               ]hexatetraconta-1,8(37),9,11,13,                                              15(42),21,23,28,30,35,38,40-tridecaene-κ.sup.4 N)cobalt(II)]            hexafluoro                                                                    phosphate                                                               188   [chloro(2,21,23,29-tetramethyl-3,6,17,20,24,28,31,35-octaazaheptacyc          lo-                                                                           [20.7.7.6.sup.8,15.2.sup.3,6.2.sup.17,20.0.sup.9,14.0.sup.37,42               ]hexatetraconta-1,8(37),9,11,13,                                              15(42),21,23,28,30,35,38,40-tridecaene-κ.sup.4 N)iron(II)]              hexafluoro                                                                    phosphate                                                               189   [(23,29-dimethyl-2,21-diphenyl-3,6,17,20,24,28,31,35-octaazaheptacyc          lo- : - [20.7.7.6.sup.8,15.2.sup.3,6.2.sup.17,20.0.sup.9,14.0.sup.37          ,42 ]hexatetraconta-1,8(37),9,11,13,                                          15(42),21,23,28,30,35,38,40-tridecaene-κ.sup.4 N)nickel(II)]            hexafluoro                                                                    phosphate                                                               190   [(2,18,20,26-tetramethyl-3,6,14,17,21,25,28,32,38-nonaazapentacyclo-          Z                                                                             [17.7.7.2.sup.3,6.2.sup.14,17.1.sup.8,12 ]octatriaconta-1,8,10,12,(3          8),18,20,25,27,32-                                                            nonaene-κ.sup.4 N)nickel(II)] hexafluorophosphate                 191   [(2,18,20,26-tetramethyl-3,6,14,17,21,25,28,32,38-nonaazapentacyclo-          `                                                                             [17.7.7.2.sup.3,6.2.sup.14,17.1.sup.8,12 ]octatriaconta-1,8,10,12(38          ),18,20,25,27,32-                                                             nonaene-κ.sup.4 N)cobalt(II)] hexafluorophosphate                 192   [(2,9,10,17,19,25,33,34-octamethyl-29-(1-methyl-2-pyridinio)-3,6,13,          16,20                                                                         24,27,31-octaazapentacyclo[16.7.7.2.sup.8,11.2.sup.3,6.2.sup.13,16            ]octatriaconta-                                                               1,8,10,17,19,24,26,31,33-nonaene-κ.sup.4 N)nickel(II)]                  hexafluorophosphate                                                     193   [(2,21,23,29-tetramethyl-33-(1-methyl-2-pyridinio)-3,6,17,20,24,28,3          1,35-                                                                         octaazaheptacyclo[20.7.7.6.sup.  8,15.2.sup.3,6.2.sup.17,20.0.sup.9,          14.0.sup.37,42 ]hexatetraconta-                                               1,8(37),9,11,13,15(42),21,23,28,30,35,38,40-tridecaene-κ.sup.4           N)nickel(II)]                                                                hexafluorophosphate                                                     194   [(3,11,14,20,24,24-hexamethyl-2,12-diphenyl-3,11,15,19,22,26-hexa-            azatricyclo[11.7.7.1.sup.5.9 ]octacosa-1,5,7,9(28),12,14,19,21,26-no          naene-κ.sup.4 N)                                                        nickel(II)] hexafluorophosphate.                                        195   [(3,11,14,20,24,24-hexamethyl-2,12-diphenyl-3,11,15,29,22,26-hexa-            azatricyclo[11.7.7.1.sup.5.9 ]octacosa-1,5,7,9(28),12,14,19,21,26-no          naene-)]                                                                      hexafluorophosphate.                                                    196   [(3,11,14,20,24,24-hexamethyl-2,12-diphenyl-3,11,15,19,22,26-hexa-            azatricyclo[11.7.7.1.sup.5.9 ]-octacose-1,5,7,9(28),12,14,19,21,26-n          onaene-                                                                       κ.sup.4 N)iron(II)] hexafluorophosphate.                          197   2,17-di(n-heptadecyl)-9,10,19,25,33,34-hexamethyl-3,6,13,16,20,24,27          ,31-                                                                          octaazapentacyclo[16.7.7.2.sup.8,11.2.sup.3,6.2.sup.13,16 ]octatriac          onta-1,8,10,17,19,24,                                                         26,31,33-nonaene-κ.sup.4 N)nickel(II)] hexafluorophosphate        198   [(9,10,19,25,41,42-hexamethyl-3,6,13,16,20,24,27,31-octaazahexa-              cyclo[16.8.sup.2,17.7.7.2.sup.8,11.2.sup.3,6.2.sup.13,16 ]hexatetrac          onta-1,8,10,17,19                                                             24,26,31,41-nonaene-κ.sup.4 N)nickel(II)] hexafluorophosphate           i                                                                       199   [(2,3,14,15,17,23-hexamethyl-3,14,18,22,25,29-hexaaazabicyclo                 [14.7.7]triaconta-1,15,17,22,24,29-hexaene-κ.sup.4 N)nickel(II          )]                                                                            hexafluorophosphate -200 [(2,3,14,15,17,23-hexamethyl-3,14,18,22,25,          29-hexaazabicyclo                                                             [14.7.7]triaconta-1,15,17,22,24,29-hexaene-κ.sup.4 N)cobalt(II          )]                                                                            hexafluorophosphate                                                     __________________________________________________________________________

    TABLE 3      FORMULAE I AND IA Compd.           No. M.sup.n+ X Y R.sub.1 R.sub.2     R.sub.3 R.sub.4 R Anion Z       1 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3     CH.sub.3 (CH.sub.2)HD 3 PF.sub.6 -- 2 Co.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 PF.sub.6     CH.sub.3 CN 3 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 PF.sub.6 Cl 4 Ni.sup.2+ (CH.sub.2).sub     .3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.4 PF.sub.6 -- 5     Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H     (CH.sub.2).sub.4 PF.sub.6 Cl 6 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.     3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.4 PF.sub.6 -- 7 Co.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2)     .sub.4 PF.sub.6 -- 8 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.4 PF.sub.6 Cl 9 Ni.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ H (CH.sub.2).sub.4     PF.sub.6 -- 10 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     φ H (CH.sub.2).sub.4 PF.sub.6 CH.sub.3      CN 11 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ     CH.sub.3 (CH.sub.2).sub.4 PF.sub.6 -- 12 Co.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 φ CH.sub.3 (CH.sub.2).sub.4 PF.sub.6 --     13 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ CH.sub.3     (CH.sub.2 ).sub.4 PF.sub.6 Cl 14 Cu.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).su     b.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.4 PF.sub.6 Cl 15     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 C(CH.sub.3).sub.3     H (CH.sub.2).sub.4 PF.sub.6 -- 16 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).s     ub.3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.5 PF.sub.6 -- 17 Co.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.5     PF.sub.6 -- 18 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     CH.sub.3 H (CH.sub.2).sub.5 Cl Cl 19 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2     ).sub.3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.5 PF.sub.6 CO/Py 20     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3     (CH.sub.2).sub.5 PF.sub.6 -- 21 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub     .3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.5 PF.sub.6 -- 22 Fe.sup.2+      (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2     ).sub.5 PF.sub.6 Cl 23 Co.sup.3+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.5 PF.sub.6 (NCS).sub.2 24     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ H (CH.sub.2)     .sub.5 PF.sub.6 -- 25 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 φ H (CH.sub.2).sub.5 PF.sub.6 -- 26 Ni.sup.2+ (CH.sub.2).sub     .3 (CH.sub.2).sub.3 H CH.sub.3 φ CH.sub.3 (CH.sub.2).sub.5 PF.sub.6     -- 27 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ     CH.sub.3 (CH.sub.2).sub.5 PF.sub.6 -- 28 Fe.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 φ CH.sub.3 (CH.sub.2).sub.5 PF.sub.6 Cl     29 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 C(CH.sub.3).sub     .3 H (CH.sub.2).sub.5 PF.sub.6 -- 30 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2     ).sub.3 H CH.sub.3 C(CH.sub.3).sub.3 H (CH.sub.2).sub.5 PF.sub.6     CH.sub.3 CN 31 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     CH.sub.3 H (CH.sub.2).sub.6 PF.sub.6 -- 32 Co.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.6 PF.sub.6 -- 33     Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H     (CH.sub.2).sub.6 PF.sub.6 Cl 34 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub     .3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.6 PF.sub.6 CO/Py 35 Cu.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.6     PF.sub.6 CH.sub.3      CH.sub.2 OH 36 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 -- 37 Ni.sup.2+ (CH.sub.2).su     b.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 Cl --     38 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3     CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 -- 39 Co.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 PF.sub.6     1-CH.sub.3Im 40 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 Im 41 Co.sup.2+ (CH.sub.2).su     b.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.6     PF.sub.6 Py 42 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 NCS 43 Co.sup.3+ (CH.sub.2).s     ub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.6     PF.sub.6 (NCS).sub. 2 44 Co.sup.3+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 (NCO).sub.2 45     Co.sup.3+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3     (CH.sub.2).sub.6 PF.sub.6 (N.sub.3).sub.2 46 Fe.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 PF.sub.6     Cl 47 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3     CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 CO/CH.sub.3      CN 48 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3     CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 CO/Py 49 Fe.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 PF.sub.6     CO/1-CH.sub.3Im 50 Fe.sup.3+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 Cl 51 Mn.sup.2+     (CH.sub.2).sub.3 (CH.sub. 2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2     ).sub.6 PF.sub.6 Cl 52 Mn.sup.3+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 Cl 53 Cu.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2)     .sub.6 PF.sub.6 Cl 54 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 φ H (CH.sub.2).sub.6 PF.sub.6 -- 55 Co.sup.2+ (CH.sub.2).sub     .3 (CH.sub.2).sub.3 H CH.sub.3 φ H (CH.sub.2).sub.6 PF.sub.6 -- 56     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ CH.sub.3     (CH.sub.2).sub.6 PF.sub.6 -- 57 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub     .3 H CH.sub.3 φ CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 -- 58 Fe.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ CH.sub.3 (CH.sub.2).su     b.6 PF.sub.6 Cl 59 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 φ CH.sub.2 φ (CH.sub.2).sub.6 PF.sub.6 Cl 60 Ni.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 C(CH.sub.3).sub.3 H     (CH.sub.2).sub.6 PF.sub.6 -- 61 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub     .3 H CH.sub.3 C(CH.sub.3).sub.3 H (CH.sub.2).sub.6 PF.sub.6 -- 62     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 (CH.sub.2).sub.6     CH.sub.3 H (CH.sub.2).sub.6 PF.sub.6 -- 63 Ni.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 H CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 -- 64     Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 H CH.sub.3     (CH.sub.2).sub.6 PF.sub.6 CH.sub.3 CN 68 Ni.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.7 PF.sub.6 -- 69     Co.sup.2+ (CH.sub.2 ).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H     (CH.sub.2).sub.7 PF.sub.6 CH.sub.3 CN 70 Ni.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.7 PF.sub.6     -- 71 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3     CH.sub.3 (CH.sub.2).sub.7 PF.sub.6 -- 72 Co.sup.3+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.7 PF.sub.6     (NCS).sub.2 73 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     φ H (CH.sub.2).sub.7 PF.sub.6 -- 74 Co.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 φ H (CH.sub.2).sub.7 PF.sub.6 -- 75     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ CH.sub.3     (CH.sub.2).sub.7 PF.sub.6 -- 76 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub     .3 H CH.sub.3 φ CH.sub.3 (CH.sub.2).sub.7 PF.sub.6 -- 77 Ni.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 C(CH.sub.3).sub.3 H     (CH.sub.2).sub.7 PF.sub.6 -- 78 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub     .3 H CH.sub.3 C(CH.sub.3).sub.3 H (CH.sub.2).sub.7 PF.sub.6 -- 80     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H     (CH.sub.2).sub.8 PF.sub.6 -- 81 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub     .3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.8 PF.sub.6 -- 82 Ni.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2)     .sub.8 PF.sub.6 -- 83 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.8 PF.sub.6 CH.sub.3 CN 84     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ H (CH.sub.2)     .sub.8 PF.sub.6 -- 85 Co.sup.2+  (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 φ CH.sub.3 (CH.sub.2).sub.8 PF.sub.6 CH.sub.3 CN 86     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H     m-xylylene PF.sub.6 -- 87 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 H m-xylylene PF.sub.6 CH.sub.3 CN 88 Fe.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H m-xylylene     PF.sub.6 Cl 89 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     CH.sub.3 H m-xylylene PF.sub.6 CO/Py 90 Fe.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H m-xylylene PF.sub.6 CO/1-CH.sub.3I     m 91 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H     m-xylylene PF.sub.6 CO/Im 92 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3     H CH.sub.3 CH.sub.3 H m-xylylene PF.sub.6 CO/4-NH.sub.2Py 93 Ni.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub. 3 CH.sub.3 CH.sub.3 m-xylylen     e PF.sub.6 -- 94 Co.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     CH.sub.3 CH.sub.3 m-xylylene PF.sub.6 H.sub.2      O 95 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3     CH.sub.3 m-xylylene PF.sub.6 Cl 96 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).     sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 m-xylylene PF.sub.6 CO/1-CH.sub.3Im     97 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3     CH.sub.3 m-xylylene PF.sub.6 CO/CH.sub.3      CN 98 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3     CH.sub.3 m-xylylene PF.sub.6 CO/Im 99 Fe.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 m-xylylene PF.sub.6     CO/4-NH.sub.2Py 100 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 CH.sub.3 m-xylylene PF.sub.6 Cl 101 Mn.sup.2+ (CH.sub.2     ).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 m-xylylene PF.sub.     6 -- 102 Mn.sup.3+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3     CH.sub.3 m-xylylene PF.sub.6 Cl 103 Cu.sup.2+ (CH.sub.2).sub.3 (CH.sub.2)     .sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 m-xylylene PF.sub.6 CH.sub.3 CN 104     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 (CH.sub.2     ).sub.3 CH.sub.3 m-xylylene PF.sub.6 -- 105 Ni.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 CN m-xylylene     PF.sub.6 -- 106 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     CH.sub.3 CH.sub.2      φ m-xylylene PF.sub.6 -- 107 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).s     ub.3 H CH.sub.3 CH.sub.3 CH.sub.2 φ m-xylylene PF.sub.6 CH.sub.3 CN     108 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 H CH.sub.3     m-xylylene PF.sub.6 -- 109 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 (CH.sub.2).sub. 6 CH.sub.3 H m-xylylene PF.sub.6 -- 110     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 (CH.sub.2).sub.6     CH.sub.3 CH.sub.3 m-xylylene PF.sub.6 -- 111 Fe.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 (CH.sub.2).sub.6      CH.sub.3 CH.sub.3 m-xylylene PF.sub.6 Cl 112 Ni.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 φ H m-xylylene PF.sub.6 -- 113 Co.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ H m-xylylene PF.sub.6     CH.sub.3 CN 114 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     φ CH.sub.3 m-xylylene PF.sub.6 -- 115 Co.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 φ CH.sub.3 m-xylylene PF.sub.6 -- 116     Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ CH.sub.3     m-xylylene PF.sub.6 CH.sub.3      CN 117 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ     CH.sub.2 φ m-xylylene PF.sub.6 -- 118 Fe.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 φ CH.sub.2 φ m-xylylene PF.sub.6     CH.sub.3 CN 119 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     p-MeOφ CH.sub.3 m-xylylene PF.sub.6 Cl 120 Fe.sup.2+ (CH.sub.2).sub.3      (CH.sub.2).sub.3 H CH.sub.3 p-Clφ CH.sub.3 m-xylylene PF.sub.6 Cl     121 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 p-Fφ     CH.sub.3 m-xylylene PF.sub.6 Cl 122 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2)     .sub.3 H CH.sub.3 3,5-diMeOφ CH.sub.3 m-xylylene PF.sub.6 Cl 125     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H     p-xylylene PF.sub.6 -- 126 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 H p-xylylene PF.sub.6 Cl 127 Fe.sup.2+ (CH.sub.2).sub.3      (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H p-xylylene PF.sub.6 CO/CH.sub.3     CN 128 Fe.sup. 2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3     H p-xylylene PF.sub.6 CO/Py 129 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub     .3 H CH.sub.3 CH.sub.3 H p-xylylene PF.sub.6 CO/1-CH.sub.3Im 130     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3     p-xylylene PF.sub.6 -- 131 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 H (CH.sub.2).sub.3(9,9-flourylene) PF.sub.6 --         (     CH.sub.2).sub.3 132 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 H (CH.sub.2).sub.3(9,9-flourylene) Cl Cl     (CH.sub.2).sub.3 133 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 H (CH.sub.2).sub.3(9,9-flourylene) PF.sub.6 CO/Py        (CH.sub.2).sub.3 134 Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 H (CH.sub.2).sub.3(9,9-flourylene) PF.sub.6 CO/1-CH.sub     .3Im         (CH.sub.2).sub.3 135 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).s     ub.3 H CH.sub.3 CH.sub.3 H CH(COOCH.sub.3)(CH.sub.2).sub.4 PF.sub.6 --     136 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H     CH.sub.2(1,3-cyclohexy- PF.sub.6 --         lene)CH.sub.2 137 Ni.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 φ CH.sub.3 (CH.sub.2).su     b.2 C(CH.sub.3).sub.2 (CH.sub.2).sub.2 PF.sub.6 -- 138 Ni.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (5-methoxy     - PF.sub.6 --         m-xylylene) 139 Ni.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.2      S(CH.sub.2).sub.2 PF.sub.6 -- 140 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).     sub.3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.2 S(CH.sub.2).sub.3 PF.sub.6     --  141 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3     CH.sub.3      ##STR8##      PF.sub.6 --  142 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     CH.sub.3 CH.sub.3      ##STR9##      PF.sub.6 --  143 Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3     CH.sub.3 H (CH.sub.2).sub.3 NH(CH.sub.2).sub.3 PF.sub.6 -- 144 Ni.sup.2+     (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.3     NCH.sub.3 (CH.sub.2).sub.3 PF.sub.6 -- 145 Co.sup.2+ (CH.sub.2).sub.3     (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H (CH.sub.2).sub.3 NCH.sub.3     (CH.sub.2).sub.3 PF.sub.6 --      164 Ni.sup.2+     ##STR10##      (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.5 PF.sub.6     --  165 Ni.sup.2+ " (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3     (CH.sub.2).sub.6 PF.sub.6 -- 166 Co.sup.2+ " (CH.sub.2).sub.3 H CH.sub.3     CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 -- 167 Ni.sup.2+ " (CH.sub.2)     .sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 m-xylylene PF.sub.6  168 Co.sup.2+      ##STR11##      (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 PF.sub.6      169 Ni.sup.2+ (CH.sub.2).sub.2 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3     CH.sub.3 (CH.sub.2).sub.6 PF.sub.6 -- 170 -- (CH.sub.2).sub.3 (CH.sub.2).     sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.4 PF.sub.6 -- 171     Fe.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 H     m-xylylene Cl Cl 172 Zn.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H     CH.sub.3 CH.sub.3 H (CH.sub.2).sub.3(9,9- Cl --         flourylene)(CH.su     b.2).sub.3 194 Ni.sup.2+ CH.sub.2 C(CH.sub.3).sub.2      CH.sub.2 (CH.sub.2).sub.3 H CH.sub.3 φ CH.sub.3 m-xylylene PF.sub.6     -- 195 -- " " " " " " " " -- 196 Fe.sup.2+ " " " " " " " " -- 199     Ni.sup.2+ (CH.sub.2).sub.3 (CH.sub.2).sub.3 H CH.sub.3 CH.sub.3 CH.sub.3     (CH.sub.2).sub.10 PF.sub.6 -- 200 Co.sup.2+ " "  " " " " PF.sub.6     --

                                      TABLE 4                                     __________________________________________________________________________    FORMULA II                                                                    Cmpd.                                                                         No. M.sup.n+                                                                         X   Y   R.sub.1                                                                         R.sub.2                                                                          R.sub.4                                                                         R.sub.5                                                                           R      Anion                                                                             Z                                        __________________________________________________________________________    65(c)                                                                             Ni.sup.2+                                                                        (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         H (CH.sub.2).sub.6                                                                  (CH.sub.2).sub.6                                                                     PF.sub.6                                                                          --                                       66  Ni.sup.2+                                                                        (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         H (CH.sub.2).sub.7                                                                  (CH.sub.2).sub.6                                                                     PF.sub.6                                                                          --                                       67  Ni.sup.2+                                                                        (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         H (CH.sub.2).sub.8                                                                  (CH.sub.2).sub.6                                                                     PF.sub.6                                                                          --                                       79  Ni.sup.2+                                                                        (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         H (CH.sub.2).sub.8                                                                  (CH.sub.2).sub.7                                                                     PF.sub.6                                                                          --                                       123 Ni.sup.2+                                                                        (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         H (CH.sub.2).sub.8                                                                  m-xylylene                                                                           PF.sub.6                                                                          --                                       124 Ni.sup.2+                                                                        (CH.sub. 2).sub.3                                                                 (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         H (CH.sub.2).sub.7                                                                  m-xylylene                                                                           PF.sub.6                                                                          --                                       __________________________________________________________________________

                                      TABLE 5                                     __________________________________________________________________________    FORMULAE III AND IIIA                                                         Cmpd.                                                                         No. M.sup.n+                                                                          X   Y   R.sub.1                                                                         R.sub.2                                                                          R.sub.4                                                                             R.sub.6                                                                          R.sub.5                                                                           Anion                                                                             Z                                       __________________________________________________________________________    146(c)                                                                            Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3                                                                         (CH.sub.2).sub.5                                                                  PF.sub.6                                                                          --                                      147(c)                                                                            Co.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3                                                                         (CH.sub.2).sub.5                                                                  PF.sub.6                                                                          CH.sub.3 CN                             148(c)                                                                            Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                            H  (CH.sub.2).sub.6                                                                  PF.sub.6                                                                          --                                      149(c)                                                                            Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3                                                                         (CH.sub.2).sub.6                                                                  PF.sub.6                                                                          --                                      150(c)                                                                            Co.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3                                                                         (CH.sub.2).sub.6                                                                  PF.sub.6                                                                          CH.sub.3 CN                             151 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         H     CH.sub.3                                                                         (CH.sub.2).sub.7                                                                  PF.sub.6                                                                          --                                      152 Co.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         H     CH.sub.3                                                                         (CH.sub.2).sub.7                                                                  PF.sub.6                                                                          --                                      153 Fe.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         H     CH.sub.3                                                                         (CH.sub.2).sub.7                                                                  PF.sub.6                                                                          Cl                                      154 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         (CH.sub.2).sub.2 CH.sub.3                                                           H  (CH.sub.2).sub.7                                                                  PF.sub.6                                                                          --                                      155 Co.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         (CH.sub.2).sub.2 CH.sub.3                                                           H  (CH.sub.2).sub.7                                                                  PF.sub.6                                                                          CH.sub.3 CN                             156 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.2 φ                                                                      H  (CH.sub.2).sub.7                                                                  PF.sub.6                                                                          --                                      157 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3                                                                         (CH.sub.2).sub.7                                                                  PF.sub.6                                                                          --                                      158 Co.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2 ).sub.3                                                                 H CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3                                                                         (CH.sub.2).sub.7                                                                  PF.sub.6                                                                          H.sub.2 O                               159 Fe.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3                                                                         (CH.sub.2).sub.7                                                                  PF.sub.6                                                                          Cl                                      160 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                            H  (CH.sub.2).sub.8                                                                  PF.sub.6                                                                          --                                      161 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3                                                                         (CH.sub.2).sub.8                                                                  PF.sub.6                                                                          --                                      162 Co.sup.2+                                                                         (CH.sub.2).sub.3                                                                  (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3                                                                         (CH.sub.2).sub.8                                                                  PF.sub.6                                                                          Cl                                      __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________    FORMULAE XVIII AND XVIIIA                                                     Cmpd.                                                                         No. M.sup.n+                                                                          X         Y   R.sub.1                                                                         R.sub.2                                                                          R.sub.3                                                                            D        Anion                                                                             Z                                __________________________________________________________________________    173 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           1,3-phenylene                                                                          PF.sub.6                                                                          --                               174 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           1,3-phenylene                                                                          Cl  --                               175 Co.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           1,3-phenylene                                                                          PF.sub.6                                                                          CH.sub.3 OH                      176 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           1,4-phenylene                                                                          PF.sub.6                                                                          --                               177 Co.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           1,4-phenylene                                                                          PF.sub.6                                                                          --                               178 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                            ##STR12##                                                                             PF.sub.6                                                                          --                               179 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           "        Cl  --                               180 Co.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           "        PF.sub.6                                                                          --                               181 Fe.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           "        PF.sub.6                                                                          Cl                               182 Fe.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           "        PF.sub.6                                                                          H.sub.2 O                        183 Cu.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           "        PF.sub.6                                                                          --                               184 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         φ                                                                              "        PF.sub.6                                                                          --                               185 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           9,10-anthracene                                                                        PF.sub.6                                                                          --                               186 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           "        Cl  --                               187 Co.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           "        PF.sub.6                                                                          CH.sub.3 OH                      188 Fe.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           "        PF.sub.6                                                                          Cl                               189 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         φ                                                                              "        PF.sub.6                                                                          --                               190 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           2,6-pyridylene                                                                         PF.sub.6                                                                          --                               191 Co.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           "        PF.sub.6                                                                          --                               192 Ni.sup.2+                                                                          ##STR13##                                                                              (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                            ##STR14##                                                                             PF.sub.6                             193 Ni.sup.2+                                                                         "         (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         CH.sub.3                                                                           9,10-anthracene                                                                        PF.sub.6                                                                          --                               197 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                          -n-C.sub.17 H.sub.35                                                               ##STR15##                                                                             PF.sub.6                                                                          --                               198 Ni.sup.2+                                                                         (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                  H CH.sub.3                                                                         (CH.sub.2).sub.8 bridge                                                             ##STR16##                                                                             PF.sub.6                                                                          --                               __________________________________________________________________________

EXAMPLE I[(2,11,13,19-Tetramethyl-3,10,14,18,21,25-hexaazabicyclo-[10.7.7]-hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)nickel(II)] Hexafluorophosphate formerly designated(2,11,20,26-Tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaeneN₄)nickel(II) Hexafluorophosphate)

This is compound 31 in Tables 2 and 3.

To a solution of 20 g of (2,12-dimethyl-3,11-bis[1-methoxyethylidene]-1,5, 9, 13-tetraazacyclohexadeca-1, 4, 9, 12-tetraene N₄)nickel(II)hexafluorophosphate (28 mmole) in 1 L of acetonitrile was added,dropwise with stirring, to a solution of 3.3 g (28 mmole) of1,6-hexanediamine in 1 L of acetonitrile. The resultant red solution wastaken to dryness on a rotary evaporator and the residue redissolved in25 ml of acetonitrile. This solution was chromatographed on a column ofWoelm neutral alumina (2.5 cm by 20 cm), eluting with acetonitrile. Theyellow band was collected and the solvent was removed by rotaryevaporation. The residue was slurried with ethanol and the product wasisolated by suction filtration, washed with ether and dried in vacuo.Yield: 19 g (90%).

EXAMPLE II[(2,12,14,20-Tetramethyl-3,11,15,19,22,26-hexaazapentacyclo[11.7.7.4⁷,7.4²⁸,29.4³⁰,31]nonatriconta-1,12,14,19,21,26,28(29),30(31),32,34,36,38-dodecaene-κ.sup.4N)nickel(II)] Hexafluorophosphate formerly designated (2,12,21,27-Tetramethyl-3,11,15,19,22,26-hexaazapentacyclo[11.7.7.4⁷,7.4²⁸,29.4³⁰,31] nonatriaconta-1,12,14,19,21,26,28(29),30(31),32,34,36,38-dodecaene N₄)nickel(II)Hexafluorophosphate)

This is compound 131 in Tables 2 and 3.

A solution of 1.98 g (7.1 mmoles) of 9,9-bis(3-aminopropyl)fluorene in500 ml of acetonitrile was added dropwise to 5.03 g (7.1 mmoles) of(2,12-dimethyl-3, 11-bis[1-methoxyethylidene]-1, 5, 9,13-tetraazacyclohexadeca-1, 4, 9, 12-tetraene N₄) nickel(II)hexafluorophosphate in 500 ml of acetonitrile. The color changed fromyellow-green to orange upon addition of the diamine. The solution wasreduced in volume to 30 ml and then passed through a column (11/2"diameter, 6" length) of alumina with acetonitrile. The solvent wasevaporated, methanol (200 ml) was added and the solution was filtered toobtain a yellow powder. Yield 3.92 g (60%).

EXAMPLE III[(2,3,11,12,14,20-Hexamethyl-3,11,15,19,22,26-hexaazatricyclo-[11.7.7.1.sup.5,9] octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)nickel(II)]Hexafluorophosphate formerly designated (2, 3, 11, 12, 21,27-Hexamethyl-3, 11, 15, 19, 22, 26-hexaazatricyclo[11.7.7.1⁵,9 ]octacosa-1, 5, 7, 9(28), 12, 14, 19, 21, 26-nonaene N₄)nickel(II)Hexafluorophosphate)

This is compound 93 in Tables 2 and 3.

To 4.41 g (6.24 mmole) of (2,12-dimethyl-3,11-bis[1-methylaminoethylidene]-1, 5, 9, 13-tetraazacyclohexadeca-1, 4,9, 12-tetraene N₄)nickel(II) hexafluorophosphate in 400 ml ofacetonitrile was added 0.30 g (13.7 mmole) of sodium metal in 25 ml ofmethanol. This solution was brought to reflux under an atmosphere ofnitrogen and a solution of α, α'-dibromo-m-xylene, 1.80 g (6.24 mmole),in 125 ml of acetonitrile was slowly added dropwise with stirring. Thesolution turned from red-purple to light orange during the addition anda white precipitate of sodium bromide formed. The solution was refluxedfor 2 hrs, then cooled and filtered. The filtrate was concentrated toabout 50 ml on a rotary evaporator and methanol was added to the cloudpoint. Upon standing, the yellow microcrystalline product precipitatedand was collected by suction filtration, washed with ether and dried invacuo at 50° C. Yield: 3.41 g (68%).

EXAMPLE IV [(13,19-Dimethyl-2,11-diphenyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)nickel(II)] Hexafluorophosphateformerly designated(2,11-Diphenyl-20,26-dimethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaeneN₄)nickel(II) Hexafluorophosphate)

This is compound 54 in Tables 2 and 3 and this Example illustrates theseveral steps which are necessary to replace a methyl group R₃ in acompound of Formula V shown in FIG. 3 with a phenyl group in order toprepare a compound of Formula I having R₃ =phenyl.

As shown in FIG. 3, this synthesis begins with the anion of Formula XII,which is actually a species of Formula V in which R₁ =H, R₂ =R₃ =CH₃.The anion of Formula XII is first deacetylated with p-toluene sulfonicacid, then treated with ammonium hexafluorophosphate to produce thecompound of Formula XIII. A sample (19.4 g, 0.05 mole) of(3,11-diacetyl-2,12-dimethyl-1,5,9,13-tetraazacyclohexadeca-1,3,9,11-tetraenatoN₄)nickel(II) (Formula XII) and 19.0 g of p-toluene sulfonic acidmonohydrate (0.1 mole) were refluxed in 200 ml of methanol for 5minutes. The heat was removed and a solution of 8 g of NH₄ PF₆ (0.11mole) in 50 ml of H₂ O was added to the reaction mixture. The flask waskept in a freezer for crystallization. After five hours, 27.5 g ofyellow crystals were isolated by filtration, washed with methanol anddried in vacuo over P₄ O₁₀. Yield: 93%.

The cationic complex of the compound of Formula XIII was thendeprotonated with sodium methoxide. For this purpose, a sample of(2,12-dimethyl-1,5,9,13-tetraazacyclohexadeca-1,4,9,12-tetraeneN₄)nickel(II) hexafluorophosphate (Formula XIII)(11.92 g, 0.02 mole) wasslurried in a solution containing 0.045 mole of sodium methoxide (from 1g of sodium) in 50 ml of methanol. The mixture was slurried for 5minutes and left in the freezer for crystallization. After 1 hour thevery dark crystalline product was filtered and washed with a smallamount of cold methanol. Yield: 5.5 g (90%). of the compound of FormulaXIV.

Reaction of this intermediate with benzoyl chloride yielded thedi-benzoyl-Jager complex of Formula XV. This reaction was effected inthe following manner. Benzoyl chloride (0.022 mole) was added to astirred mixture of 3.05 g (0.01 mole) of(2,12-dimethyl-3,11-dibenzoyl-1,5,9,13-tetraazacyclohexadeca-1,3,9,11-tetraenatoN₄)nickel(II) (Formula XIV) and 3.31 ml (0.024 mole) of triethylamine in300 ml of ethyl ether. The deep red color changed immediately to orangeand the precipitation of the orange product and Et₃ NHCl occurred. After30 minutes, the solids were filtered and washed with water. The etherfiltrate was evaporated to dryness and the residue was combined with thesolid product. The combined solids were dissolved in chloroform andchromatographed on alumina. The red-orange eluent solution (chloroformsolvent) was evaporated and the residue recrystallized from adichloromethane-ethyl ether mixture. Yield: 80%.

The salt of Formula I containing the substituted methyl vinyl etherfunctional group was prepared by reaction with CH₃ SO₃ F as describedabove. Ring closure proceeded as follows. A solution of 0.002 mole ofthe methyl vinyl ether complex in 200 ml of CH₃ CN and 0.0022 mole of1,6-diaminohexane in 200 ml of acetonitrile were simultaneously added ata slow rate to a third vigorously stirred 200 ml volume of acetonitrile,using a peristaltic pump. The volume of the solution was then reduced toabout 30 ml by rotary evaporation at about 30° C. The resulting solutionwas chromatographed on an alumina column (2.5 cm by 20 cm) usingacetonitrile. A yellow band was collected and its volume reduced toabout 30 ml. The addition of ethanol followed by further evaporation ledto precipitation of the product. Yield: 82%.

EXAMPLE V[(2,3,9,10,12,18-Hexamethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]-pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)nickel(II)] Hexafluorophosphate formerly designated(2,3,9,10,19,25-Hexamethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaeneN₄)nickel(II) Hexafluorophosphate)

This is compound 20 in Tables 2 and 3.

10.9 Gram of(2,12-dimethyl-3,11-bis[1-methylaminoethylidene]-1,5,9,13-tetraazacyclohexadeca-1,4,9,12-tetraeneN₄)nickel(II) hexafluorophosphate (15.4 mmole) was dissolved in 500 mlof acetonitrile under nitrogen in a 2 L, 3-necked, round-bottomed flaskequipped with a condenser, stirbar, and a 1 L dropping funnel. Asolution of 6.37 g of 1,5-bis(para-toluene-sulfonato)pentane (15.4mmole) dissolved in 500 ml of acetonitrile was placed in the droppingfunnel. A solution of 0.71 g of sodium metal (30.8 mmole) in 25 ml ofmethanol was added to the solution of the nickel complex, whereupon thecolor turned deep red. The solution was brought to reflux under nitrogenand the solution of the ditosylate was slowly added over a 4 hr period,after which time the solution turned dark yellow-red and a whitecrystalline precipitate of sodium para-toluenesulfonate had formed. Thesolution was concentrated on a rotary evaporator to about 100 ml andfiltered through celite. Two hundred and fifty ml of methanol, saturatedwith ammonium hexafluorophosphate, was slowly added and the solution wasrotary evaporated to give the yellow microcrystalline product. Yield:9.1 g (76%). Sometimes the product was dark brown and waschromatographed on alumina, eluting with acetonitrile.

EXAMPLE VI[(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,24-hexaazabicyclo[10.7.6]pentacosa-1,11,13,18,20,24-hexaene-κ⁴N)nickel(II)] Hexafluorophosphate formerly designated(2,3,10,11,19,25-Hexamethyl-3,10,14,17,20,24-hexaazabicyclo[10.7.6]pentacosa-1,11,13,17,19,24-hexaeneN₄)nickel(II)Hexafluorophosphate)

This is compound 169 in Tables 2 and 3 having X═(CH₂)₂.

This 15-membered macrocyclic dry cave complex was prepared by dissolving5.0 g (7.19 mmole) of(2,11-dimethyl-3,11-bis[1-methoxyethylidene]-1,5,8,12-tetraazacyclopentadeca-1,4,8,11-tetraeneN₄)nickel(II) hexafluorophosphate in 500 ml of acetonitrile and slowlyadding a solution of 1.04 g (7.19 mmole) ofN,N'-dimethyl-1,6-hexanediamine in 500 ml of acetonitrile. The solutionturned a dark brown-red and was rotary evaporated to give a viscous darkred oil which was dissolved in a minimum amount of acetone andchromatographed on an alumina column (3" wide by 12-15 inches long)eluting slowly with a 1:1 mixture of acetone and dichloromethane. Thelight yellow band was collected, leaving numerous dark bands at the topof the column, rotary evaporated to dryness and slurried with absoluteethanol. The product was isolated by suction filtration, washed withether, and then dried in vacuo. Yield: 1.0 g (18%).

EXAMPLE VII[(14,20-Dimethyl-3,11,15,19,22,26-hexaazatricyclo[11.8²,12.7.7]pentatriaconta-1,12,14,19,21,26-hexaeneκ⁴N)nickel(II)] Hexafluorophosphate formerly designated(14,20-Dimethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.8²,11]pentatriaconta(1,11,14,19,21,26-hexaeneN₄)nickel(II)Hexafluorophosphate)

This is the doubly-bridged compound 79 in Tables 2 and 4 and has theFormula XVI shown in FIG. 3. A solution of 3.05 g (0.01 mol) of theneutralized cationic complex of Example IV (Formula XIV) and 3.30 ml(0.024 mole) of triethylamine in 300 ml of ether was slowly mixed (3hrs) with a solution of 2.3 ml (0.01 mole) of sebacoyl chloride in 300ml of ether, using a peristalsic pump. Both solutions are added to athird portion of 300 ml of ether which is stirred vigorously in a roundbottomed, 3-necked flask. The reaction was carried out under nitrogenand the product was isolated and purified like the usual Jager complexesof nickel(II). Yield: 3.0 g (70%).

This compound was converted into the corresponding methoxy compound inthe usual way; i.e., reaction with CH₃ SO₃ F, followed bycrystallization as the PF₆ salt. The product was soluble in methanol butprecipitated upon addition of ethanol.

Formation of the second bridge proceeded upon addition of 0.002 mole ofthe product described immediately above in 200 ml of CH₃ CN and 0.0022mole of 1,7-heptanediamine in 200 ml of acetonitrile, slowly andsimultaneously (4 hrs) into a vigorously stirred 200 ml volume ofacetonitrile by means of a peristaltic pump. The volume of the resultingsolution was reduced to about 30 ml on a rotary evaporator. Theconcentrated solution was loaded onto an alumina column (2.5 cm×20 cm)packed under acetonitrile, and eluted with acetonitrile. A yellow bandwas collected. After reducing the volume to 30 ml, the product wasprecipitated by the addition of methanol followed by evaporation of theacetonitrile. Yield: 48%.

EXAMPLE VIII(2,3,8,9,11,17-hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaena-κ⁴N) Hexafluorophosphate formerly designated(2,3,8,9,11,17-Hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-(1,9,11,16,18,23-hexaeneN₄) Hexafluorophosphate.)

This is compound 170 in Tables 2 and 3.

This ligand salt was prepared by bubbling a stream of hydrogen chloridegas through a solution of 2.62 g (3.44 mmole) of the correspondingnickel(II) hexafluorophosphate complex of the titled ligandhexafluorophosphate in 50 ml of acetonitrile. The solution turned bluewithin several minutes. The ligand was precipitated by slow addition ofa solution of tetrachlorozincate ions which were prepared as follows:4.37 g (68.8 mmole) of granular zinc was added to 100 ml of acetonitrileand digested with hydrogen chloride gas until no more zinc remained. Theflocculent white precipitate was filtered, washed with acetonitrile andether, and dried in vacuo. The crude ligand tetrachlorozincate salt wasdissolved in 25 ml of H₂ O. Slow addition of aqueous ammoniumhexafluorophosphate resulted in the formation of the white granularproduct which was suction filtered, washed with ether, and dried invacuo. Yield: 4.12 g (71%).

EXAMPLE IX(2,11,13,19-Tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N) Hexafluorophosphate formerlydesignated(2,11,20,26-Tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene N₄) Hexafluorophosphate)

This is the metal-free salt derived from the nickel salt prepared inExample 1 above.

A solution of 5.0 g (6.6 mmole) of the nickel salt of Example I in 100ml of acetonitrile was bubbled with hydrogen chloride gas for severalminutes until the solution was deep blue. The solvent was stripped offby rotary evaporation and the residue dissolved in 100 ml of H₂ O. Tenmilliliters of absolute ethanol was added to the solution, followed byslow addition of a solution of 10.7 g of ammonium hexafluorophosphate in50 ml of water. The off-white granular solid which formed was isolatedby suction filtration, washed with ethyl ether, and dried in vacuo.Yield: 4.48 g (80%).

EXAMPLE X[(2,3,8,9,11,17-Hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ⁴ N)cobalt(II)] Hexafluorophosphateformerly designated(2,3,8,9,18,24-Hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene N₄)cobalt(II) Hexafluorophosphate)

This is compound 7 in Tables 2 and 3. The preparation of this compound,and of the other cobalt and iron complexes in Examples XI-XV below, mustbe conducted under a nitrogen atmosphere.

This cobalt(II) complex was prepared by slurrying 2.0 g of(2,3,8,9,18,24-hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene N₄) hexafluorophosphate (2.35 mmole)in 10 ml of methanol. This mixture was stirred and warmed on a hotplate. A solution was prepared by dissolving 0.59 g (2.35 mmole) ofcobalt acetate tetrahydrate and 0.33 g (2.35 mmole) of sodium acetatetrihydrate in 25 ml of hot methanol. The two solutions were mixed andthe resulting solution turned orange. The orange microcrystallineproduct began to precipitate immediately. The solution was cooled, theproduct collected by suction filtration and washed with methanol andether and dried under vacuum. Yield: 1.54 g (86%).

EXAMPLE XI[1-Methylimidazole(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)cobalt(II)] Hexafluorophosphateformerly designated(2,3,10,11,20,26-Hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene N₄)(N-methylimidazole)cobalt(II)Hexafluorophosphate)

This compound, number 39 in Tables 2 and 3 above, was prepared byslurrying 226 mg of(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)cobalt(II) hexafluorophosphate(0.286 mmole) (this is compound 37 prepared as described in theAdditional Examples below) in 5 ml of methanol. One hundred milligrams(1.22 mmole) of N-methylimidazole was added and the solution darkenedconsiderably. The solution was heated for about 15 minutes and allowedto cool. The dark orange microcrystals were collected, washed withether, and dried in vacuo. Yield: 178 mg (71%).

EXAMPLE XII[Chloro(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1.sup.5,9] octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)] Chloridedimethanolate formerly designatedChloro(2,12,21,27-tetramethyl-3,11,15,19,22,26-hexaazatricyclo-[11.7.7.1.sup.5,9]-(octacosa-1,5,7,9(28),12,14,19,21,26-nonaeneN₄)iron(II)Chloridedimethanol)

This is compound 171 in Tables 2 and 3.

To a solution of 1.0 g (1.2 mmole) of(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaeneN₄)hexafluorophosphate(prepared by demetallation of the corresponding nickel compound(compound 86, the synthesis of which is indicated in Table 7 below) bythe method of Example VIII above) dissolved in 50 ml of acetonitrile wasadded to 0.24 g (1.2 mmole) of bis(acetonitrile)iron(II) chloride and0.35 g (3.5 mmole) of triethylamine to yield a deep red solution whichwas filtered through celite. The solution was stirred overnight duringwhich time an orange precipitate formed which was collected and dried invacuo. Yield 0.5 g (78%). Anal: Calc. for FeC₂₆ H₃₆ N₆ Cl₂ : C, 55.83;H, 6.49; N, 15.02. Found: C, 55.73; H, 6.53; N, 15.16. This product wasrecrystallized from methanol to yield large crystals of dimethanolsolvate.

EXAMPLE XIII[Chloro(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1.sup.5,9] octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]Hexafluorophosphate formerly designatedChloro(2,12,21,27-tetramethyl-3,11,15,19,22,26-hexaazatricyclo-[11.7.7.1.sup.5,9] octacosa-1,5,7,9(28),12,14,19,21,26-nonaeneN₄)iron(II)Hexafluorophosphate)

This compound, compound 88 in Tables 2 and 3, is a different salt of theiron(II) complex of Example XII. To a solution of 0.5 g (0.89 mmole) ofthe iron(II) salt of Example XII dissolved in 75 ml of methanol wasadded an excess of ammonium hexafluorophosphate dissolved in methanol toyield a red-orange microcrystalline precipitate which was collected anddried in vacuo. Yield: 0.5 g (85%).

EXAMPLE XIV[Chloro(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo-[11.7.7.1⁵,9-] octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]Hexafluorophosphate formerly designatedChloro(2,3,11,12,21,27-hexamethyl-3,11,15,19,22,26-hexaazatricyclo-[11.7.7.1⁵,9] octacosa-1,5,7,9(28),12,14,19,21,26-nonaeneN₄)iron(II)Hexafluorophosphate)

This is compound 95 in Tables 2 and 3.

To a suspension of 2.0 g (2.3 mmole) of(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1.sup.5,9] octacosa-1,5,7,9(28),12,14,19,21,26-nonaeneN₄) tetrachlorozincate in50 ml of methanol was added 0.48 g (2.3 mmole) of bis-acetonitrileiron(II) chloride and 0.92 g (9.1 mmole) of triethylamine. The solutionwas refluxed for 10 minutes then filtered through celite. After additionof 3.0 g (18.4 mmole) of ammonium hexafluorophosphate dissolved in aminimum volume of methanol the solution was allowed to stand overnight.The large red crystals which formed were collected and dried in vacuo.Yield: 1.15 g (72%).

EXAMPLE XV[Chloro(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)iron(III)] Hexafluorophosphateformerly designatedChloro(2,3,10,11,20,26-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaeneN₄)iron(III) Hexafluorophosphate)

This is compound 50 in Tables 2 and 3 and is the iron(III) salt ofFormula IA corresponding to the cobalt(II) salt of Example XI.

Under an atmosphere of nitrogen, 1.0 g (1.5 mmoles) of the iron(II)salt,chloro(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)iron(II) hexafluorophosphate, wasdissolved in 25 ml of acetonitrile. 0.26 g (1.5 mmoles) of solid NOPF₆were added to the stirred solution and the flask immediately connectedto the vacuum line to trap evolved NO gas. The solution rapidly changedcolor from red-brown to deep-blue with the evolution of a colorless gasunder partial vacuum. Evaporation of the solvent to dryness left ablue-green oily powder which can be carefully recrystallized, under N₂,from hot acetonitrile to give deep-blue blocks of crystalline material.Recrystallized yield: 0.49 g (41%).

EXAMPLE XVI[(2,12,14,20-Tetramethyl-3,11,15,19,22,26-hexaazapentacyclo[11.7.7.4⁷,7.4²⁸,29.4³⁰,31] nonatriaconta-1,12,14,19,21,26,28(29),30(31),32,34,36,38-dodecaene-κ⁴N)zinc(II) Chloride formerly designated(2,12,21,27-Tetramethyl-3,11,15,19,22,26-hexaazapentacyclo[11.7.7.4⁷,7.4²⁸,29.4³⁰,31]nonatriaconta-1,12,14,19,21,26,28(29),30(31),32,34,36,38-dodecaeneN₄)zinc(II)Chloride.)

This is compound 172 in Tables 2 and 3.

The tetrachlorozincate salt of the ligand obtained from the nickel(II)salt synthesized in Example II was dissolved in boiling acetonitrile(50-75 ml). The solution was filtered while hot and 1.0 g oftriethylamine was added. A yellow solution was obtained which yielded asolid product on standing overnight. Anal. Calcd: for the zinc complex:C, 62.31; H, 6.78; N, 11.78. Found: C, 61.65; H, 7.10; N, 11.59.

EXAMPLE XVII[(2,3,10,11,13,19-Hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)copper(II)] Hexafluorophosphateformerly designated(2,3,10,11,20,26-Hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaeneN₄)copper(II) Hexafluorophosphate)

This is compound 53 in Tables 2 and 3 and is the copper (II) saltcorresponding to the cobalt(II) salt synthesized in Example XI.

One gram (1.1 mmole) of(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N) hexafluorophosphate was slurriedin 20 ml of refluxing methanol. To this solution was added a solution of0.25 g (1.3 mmole) of copper(II) acetate hydrate and 0.46 g (3.4 mmole)of sodium acetate trihydrate dissolved in 15 ml of hot methanol. Thesolution turned brown immediately with the formation of a redcrystalline product. The product was recrystallized from anacetonitrile/ethanol solution to yield large red crystals. Yield 0.74 g(85%).

EXAMPLE XVIII[Acetonitrile(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo-[11.7.7.1⁵,9] octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)copper(II)]Hexafluorophosphate formerly designated(2,3,11,12,21,27-Hexamethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9] octacosa-1,5,7,9(28),12,14,19,21,26-nonaeneN₄)copper(II)Hexafluorophosphate, acetonitrile

This is compound 103 in Tables 2 and 3 and is the copper(II) saltcorresponding to the iron(II) salt synthesized in Example XIV. Thiscopper complex was synthesized using exactly the same proceduredescribed in Example XVII.

EXAMPLE XIX[Chloro(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)manganese(III)]Hexafluorophosphate formerly designatedChloro(2,3,10,11,20,26-Hexamethyl-3,10,14,18,21,25-Hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaeneN₄)manganese(III) Hexafluorophosphate)

This is compound 52 in Tables 2 and 3 and is the manganese (III) saltcorresponding to the cobalt (II) salt prepared in Example XI.

Under an atmosphere of nitrogen, 3.00 g (3.3 mmoles) of(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N) hexafluorophosphate hydrogenchloride was dissolved in 25 ml of acetonitrile. To this solution wasadded a solution containing 1.20 g (3.4 mmoles) oftris-2,4-pentanedionato-manganese(III) (Mn(acac)₃) in 10 ml ofacetonitrile. The resultant yellow-brown solution was warmed and stirredfor 1 hour after which the volume was reduced until a dark-browncrystalline precipitate began to appear. Addition of 5 ml ethanolproduced copious amounts of powdery brown material which was filteredand washed with toluene to remove any unreacted Mn(acac)₃. The brownmaterial may be recrystallized from acetonitrile/ethanol to givedark-brown microcrystals which may be recrystallized from acetonitrileby slow evaporation to give large rectangular blocks. Recrystallizedyield: 1.02 g (32%). The instant Mn(III) salts as in this example appearto be readily synthesized. The Mn(II) salts are most readily preparedfrom the Mn(III) salts by reduction.

ADDITIONAL EXAMPLES

For the sake of brevity, the remaining examples will be presented intabular form. Table 7 below shows the synthetic methods (Methods A-S)used to prepare all the compounds listed in Table 2 above; in the caseof those compounds which are prepared in Examples I-XIX above, Table 7refers to both one of the lettered synthetic methods described below andto the appropriate one of Examples I-XIX, though it should be noted thatthe two methods are not always the same. Table 7 also shows thetheoretical and empirically-determined analyses of each of the compoundsfor carbon, hydrogen, nitrogen and (in some cases) metal. The varioussynthetic methods referred to in Table 7 are as follows:

METHOD A

This is an example of the bridging of a compound of Formula VI with anα, Ω-diamine, as shown in FIG. 3 of the accompanying drawings.

0.01 mole of a [2,12-di-R₂ -4,10-di-R₁ -3,11-bis(1-methoxy-R³-idene)-1,5,9,13-tetraazacyclohexadeca-1,4,9,12-tetraene-N¹,N⁵,N⁹,N¹³ ]nickel(II) hexafluorophosphate and 0.01 mole of appropriate diamine R⁴NHRNHR⁴ are each dissolved in 250 mls of acetonitrile. The two solutionsare slowly (over 1 hour) dripped simultaneously into a round-bottomflask containing 250 mls of refluxing stirred acetonitrile, using aperistaltic pump. The solution is stirred at reflux for an additional 3hours before concentrating it on a rotary evaporator to about ˜30 mls.This solution is chromatographed on neutral alumina with acetonitrileeluent and the fastest moving yellow or orange band collected.Evaporation to dryness and recrystallization from acetonitrile/ethanolresults in the desired bridged complex as the hexafluorophosphate salt.

This method is described in Busch et al, J.A.C.S., 103, 1472(1981).

METHOD B

This is essentially a variant of Method A and again involves the use ofa diamine to bridge a compound of Formula VI.

Method A is followed using the appropriate primary diamine but after theproduct has been separated by the chromatography on alumina, the productmust be separated from contaminant oligomers. This is done by convertingthe hexafluorophosphate anion to chloride by dissolving the salt in dryacetone and adding acetone saturated with tetrabutylammonium chloride.The chloride salt, which precipitates immediately, is collected byfiltration and washed with acetone, then dissolved in a minimum volumeof water and loaded onto a chromotography column of CM- or SP-Sephadexion exchange resin. Elution of the desired monomer is accomplished using0.2M Na₂ SO₄ in water. The yellow band is collected and upon addition ofexcess NH₄ PF₆ in water an immediate precipitate of the desired complexforms as the hexafluorophosphate salt. This product is collected byfiltration and recrystallized from CH₃ CN/ethanol.

This method is described in Busch et al, Inorg. Chem., 20, 2384(1981).

METHOD C

This is an example of the reaction of a compound of Formula VIII with aditosylate to form a compound of Formula IX, as shown in FIG. 3 of theaccompanying drawings. The method can also be carried out using thecorresponding dichloride or dibromide.

0.01 moles of a [2,12-di-R₂ -4,10-di-R₁ -3,11-bis(1-(R⁴ amino)-R³-idene)-1,5,9,13-tetraazacyclohexadeca-1,4,9,12-tetraene-N¹,N⁵,N⁹,N¹³ ]nickel-(II) hexafluorophosphate (Formula VIII) is dissolved in 250 mlsCH₃ CN and 0.02 moles of metallic sodium dissolved in 25 mls of methanolare added. This solution and one containing 0.01 moles of an appropriatedifunctional bridge material X--R--X (X×tosylate, Cl or Br) aresimultaneously dripped into 250 mls of stirred refluxing acetonitrileusing a peristaltic pump over a period of 1 hour. The solution isstirred at reflux for at least 3 more hours before filtering to removeNaX by-product. The resultant solution is worked up exactly as describedin method A.

This method is described in the paper in J.A.C.S., 103, 1472(1981)referred to in Method A above.

Method D

This method, like several of the other methods described below, beginswith the appropriate ligand salt from which the metal has been removed.As described above, this ligand salt can be prepared by demetalling anickel or other compound of Formula VIII with hydrochloric acid andacetonitrile, followed by addition of zinc chloride to precipitate theligand tetrachlorozincate salt. Since in most cases the compounds listedin Table 2 are hexafluorophosphate salts, it is advantageous to convertthe tetrachlorozincate salt to the hexafluorophosphate salt by additionof ammonium hexafluorophosphate, as described above.

The entire procedure described in the following paragraph must becarried out under nitrogen.

0.001 mole of cobalt (II) acetate tetrahydrate and 0.004 moles of sodiumacetate trihydrate are dissolved in 25 ml of hot methanol. This solutionis added to one containing 0.001 mole of the appropriate ligand salt in25 mls of hot methanol. An immediate color change to deep yellow orangeoccurs and, often, orange products beings to precipitate. If the productdoes not volunteer from solution, addition of methanol or ethanolsaturated with NH₄ PF₆ will induce precipitation. The product iscollected by filtration, washed with ethanol and ether and vacuum dried.The orange powder may if necessary be recrystallized fromacetonitrile/ethanol.

This procedure is described in a Ph.D. dissertation by J. C. Stevens(Ohio State University, 1979) and by a post-doctoral report by M. Kojima(Ohio State University, 1980). In certain cases, the salt prepared bythis process may include ethanol or acetonitrile either as the ligand Zor as solvent of crystallization.

METHOD E

This method must also be carried out under nitrogen.

0.001 mole of the appropriate ligand salt is dissolved in 25 mls of CH₃CN and 0.002 mole of (bis-pyridine)iron(II) chloride is added as a greensolid. The slurry is stirred and 0.006 mole of triethylamine is slowlydripped in, resulting in a color change from green to deep red. Thesolution is stirred at reflux for 10 minutes before filtration andevaporation to dryness leaving a red gum. Addition of methanol orethanol causes the gum to dissolve and, frequently, precipitation of thedesired complex follows almost immediately. If not, the product may beinduced to precipitate by addition of a methanol or ethanol solutionsaturated with NH₄ PF₆. The products is collected by filtration and maybe recrystallized from CH₃ CN/ethanol.

This method is described in a PhD. dissertion by L. L. Zimmer (OhioState University, 1979).

METHOD F

This method is identical to Method E except that the(bis-pyridine)iron(II) chloride is replaced by the correspondingbis-acetonitrile salt; again, the entire procedure is carried out undernitrogen.

METHOD G

This method is generally similar to Method D, except that a copper saltis prepared instead of a cobalt salt.

0.001 mole of the appropriate ligand salt is slurried in 20 ml ofrefluxing methanol to which is then added a solution of 0.0012 mole ofcopper (II) acetate hydrate or copper(II) chloride hydrate and 0.003mole of sodium acetate trihydrate in 15 ml of hot methanol. The solutionturns brown immediately and a red crystalline product precipitates. Theproduct may be recrystallized from acetonitrile/ethanol.

This method is also described in the Zimmer dissertation referred tounder Method E above.

METHOD H

The following procedure must be carried out under nitrogen.

0.001 moles of the appropriate cobalt (II) complex (prepared by method Dabove) is dissolved in 50 mls of acetonitrile. 0.015 moles of NaX (whereX is the desired axial ligand NCS⁻, N₃ ⁻,NCO⁻) in 25 mls of water isadded. 0.001 mole of (NH₄)₂ Ce(NO₃)₆ in 10 ml of methanol is slowlydripped into the resultant mixture. The solution becomes dark and isremoved from the N₂ atmosphere, filtered, and allowed to stand for 1week whereupon the crystals which had formed were collected byfiltration. If crystals do not volunteer then water saturated with NH₄PF₆ may be slowly added to induce precipitation.

This method is described in the Stevens' dissertation referred to underMethod D above and also in a PhD. dissertation by P. J. Jackson (OhioState University, 1981).

METHOD I

The following procedure must be carried out under nitrogen.

0.001 mole of the appropriate four-coordinate cobalt(II) complex(prepared by method D above) is slurried in 20 mls methanol. 0.01 molesof the desired axial ligand B as either the neat ligand (for imidazole,N-methylimidazole or pyridine) or as the sodium salt (for ligand NCS⁻)is added and the solution refluxed for 15 minutes. Upon cooling, orangecrystals form and are collected by filtration.

This method is described in the Stevens' dissertation referred to underMethod D above.

METHOD J

The following procedure must be carried out under nitrogen.

0.001 moles of the appropriate iron(II) complex (prepared by method E orF above) are dissolved in 10 mls of CH₃ CN and a solution of 0.001 moles(NH₄)₂ Ce(NO₃)₆ in 5 mls methanol is slowly added dropwise withstirring.

This method is described in the Zimmer dissertation referred to underMethod E above.

METHOD K

The following procedure must be carried out under nitrogen.

0.001 mole of the appropriate ligand salt is dissolved in 10 mls CH₃ CNand 0.0014 mole of (tris-2,4-petanedionato)manganese(III) is added. Themixture is refluxed for 40 minutes whereupon brown micro-crystals beginto fall from solution. Addition of ethanol saturated with NH₄ PF₆induces further crystallization. The product may be collected byfiltration, washed with ethanol, toluene and either and recrystallizedfrom CH₃ CN/ethanol.

METHOD L

The following procedure must be carried out under nitrogen.

0.001 mole of the appropriate manganese(III) complex (prepared by methodK above) is dissolved in acetonitrile containing 0.1M N(CH₃)₄ PF₆. Thesolution is stirred and electrolyzed with a platinum gauze at -0.2V vsAg°/Ag⁺ until a steady coulomb count is reached. The solution brightensfrom deep red-brown to deep orange during the process of reduction. Thesolution is pumped to dryness and extensive, repeated recrystallizationsfrom acetonitrile/ethanol yield large red crystals of the desiredproduct.

METHOD M

This is an example of the conversion of a dianion of Formula X to acompound of Formula XI using a diacid chloride, as shown in FIG. 3 ofthe accompanying drawings.

0.01 moles of the appropriate [2,12-di-R₂ -4,10-di-R₁-1,5,9,13-tetraazacyclohexadeca-1,3,9,11-tetraenato] nickel (theprotonated form of a compound of Formula X) in 300 ml dry ether isstirred under nitrogen. 0.024 mole of triethylamine is added followed bythe slow dropwise addition of 0.01 mole of the appropriate diacidchloride ClOC--R₅ --COCl dissolved in 300 mls ether over a period of 3hours. The red solution and orange product are evaporated to dryness,washed with water to remove NHEt₃ Cl and dried in vacuo. Afterchromatography on neutral alumina using chloroform eluent, the redsolution is evaporated to dryness yielding red crystals of the bridgeddiketone. Methylation on the ketone oxygen atoms is carried out usingpublished procedures as for the simple unbridged Jagermolecules .0.005moles of the methylated complex in 25 mls of CH₃ CN is exposed to 0.01moles of the appropriate amine HNRR₄ in acetonitrile resulting in animmediate color change from green to deep orange-yellow. Evaporation todryness followed by recrystallization from acetonitrile/ethanol resultsin the desired retro-bridged material.

This method is described in the Kojima post-doctoral report referred tounder method D above and in a post-doctoral report by B. K. Daszkiewicz(Ohio State University, 1978).

METHOD N

The following procedure must be carried out under nitrogen.

0.001 mole of the appropriate iron(II) complex (prepared by method E orF above) and 0.010 moles of axial ligand Z are dissolved in 10 ml of CH₃CN and 60 ml of ethanol. The solution is filtered into a Schlenk flaskand removed from the nitrogen atmosphere. The flask is connected to acylinder of high-grade CO and evacuated under high vacuum. CO isintroduced at a pressure slightly above atmospheric, causing thesolution color to change from deep red to a less intense orange. Theflask is re-sealed and returned to the nitrogen atmosphere whereupon 0.5g of NH₄ PF₆ in a minimum volume of ethanol is added. This procedureyields a red-orange, generally crystalline precipitate which iscollected and washed with ethanol and ether.

This method is described in the Zimmer dissertation referred to undermethod E above.

METHOD P

Double bridged complexes of Formula II or IIA are prepared by acombination of methods B and M. The appropriate retro-bridged methylatedcomplex is prepared as described in method M and is reacted with 1equivalent of the necessary diamine H₂ N--R--NH₂ in acetonitrile asdescribed in method B. The resultant double bridged compound is workedup as described in method B on sephadex ion exchanger to remove anyunwated oligomers.

This method is described in the Kojima post-doctoral report referred tounder Method D above and in the Dasckiewicz post-doctoral reportreferred to in method M above.

METHOD Q

This method is used for the synthesis of the bis(piperazino)-bridgedcomplexes of Formulae XVIII and XVIIIA.

0.005 moles of the same starting material of Formula VI used in method Aabove are dissolved in 100 ml of acetonitrile and slowly added to asolution of 0.1 mole of piperazine in 100 ml of methanol. The orangesolution is reduced in volume and methanol added. This latter process isrepeated until orange microcrystals begin to fall from solution. Thisproduct is recrystallized from acetonitrile/methanol (1:2 v/v). 0.0012moles of this material are dissolved in 100 ml of acetonitrile; 0.0013moles of the desired difunctional bridge material X--R--X (X×Cl or Br)are dissolved in 100 ml. acetonitrile and both solutions aresimultaneously dripped into 50 ml of refluxing acetonitrile (2 hoursaddition time). The solution is stirred for an additional hour whereuponthe volume is reduced to 10 ml and 0.003 moles of triethylamine areadded. The mixture is chromatographed on neutral alumina usingacetonitrile eluent and the fastest moving band is collected. The volumeof the collected solution is reduced to 10 ml and ethanol is added toinduce crystallization of the desired product.

This method (together with methods R and S below) is described in aPh.D. dissertation by K. J. Takeuchi (Ohio State University, 1981).

METHOD R

This method is used for converting the hexafluorophosphate salts ofFormulae XVIII prepared by method Q to the corresponding chloride salts.

0.001 moles of the appropriate nickel (II) bis hexafluorophosphate saltprepared by method Q above are dissolved in a minimum volume of dryacetone. To this solution is slowly added acetone saturated withtetrabutylammonium chloride to induce immediately a voluminous yellowprecipitate which is recovered and dried in vacuo. The product may berecrystallized by dissolution in a minimum volume of dry acetonitrilefollowed by slow addition of dry acetone. The resultant dichloride saltsare usually very hygroscropic and are best stored in a vacuumdesiccator.

METHOD S

This method must be carried out under nitrogen.

The nickel hexafluorophosphate salts in Formula XVIII prepared by MethodQ above are demetallated in the manner already described usinghydrochloric acid in acetonitrile, and the free-ligand salts thusproduced are converted to the corresponding iron(II) salts using eithermethod E or method F above, except that in either case precipitation ofthe iron(II) complex salts is induced by addition of tetrabutylammoniumtetrafluoroborate in ethanol.

METHOD T

3,4-diacetyl-2,12-dihydroxy-7,7-dimethyl-5,9-diazatrideca-2,4,9,11-tetraenewas synthesized by the method described in Riley et al, InorganicSynthesis, 18, 36 (1978) and Riley, D. P., Ph.D. Thesis, The Ohio StateUniversity, Columbus, Ohio (1975), from 2,2-dimethyl-1,3-propanediamine.The product crystallized in the freezer after several hours in a yieldof 75% based upon the diamine. The product was then converted to(3,11-diacetyl-1,12-dihydroxy-7,7-dimethyl-5,9-diazatrideca-2,4,9,11-tetraenato)nickel(II)in 90% yield by the method described in the same two references. Ringclosure of the product was then effected by placing 46 grams (0.12 mole)of the product in 130 ml. of 1,3-propanediamine, freshly distilled frompotassium hydroxide. The result slurry was brought to reflux whereupon,after approximately 10 to 15 minutes, an orange solid precipitated. Thesolution was cooled, 50 ml. of water were added and the precipitate wascollected by filtration. The orange solid was washed with copiousamounts of water and dried in vacuo at room temperature to yield (3,11-diacetyl-2,7,7,12-tetramethyl-1,5,9,13-tetratriazacyclohexadeca-2,4,9,11-tetraenato)nickel(II) in a yield of 78% based upon the starting complex. The product wasdeacetylated by the procedure described in the aforementioned Riley etal paper in Inorganic Synthesis 18, 36 (1978) to produce(2,7,7,12-tetramethyl-1,5,9,13-tetraazacyclohexadeca-2,4,9,11-tetraenato)nickel(II). Next, benzoyl groups were added by dissolving 6.7 g. of thedeacetylated compound in 300 ml of ether, then adding 5.8 ml. (0.4 mole)of triethylamine, followed by dropwise addition of a mixture of 4.7 ml.(0.4 mole) of benzoyl chloride and 100 ml. of ether to the rapidlystirred solution. An orange precipitate resulted and this precipitatewas filtered, washed with water and dried and the resultant solid takenup in a small amount of chloroform and passed through a column ofalumina. The orange band was collected, the solvent evaporated andethanol added to cause the oil to solidify, giving 8 g. of(3,11-dibenzoyl-2,7,7,12-tetramethyl-1,5,9,13-tetraazacyclohexadeca-2,4,9,11-tetraenato)nickel(II). (A yield of 73% based upon the deacetylated startingmaterial.)

The carbonyl groups of this compound were methylated in the mannerdescribed in Schammel et al, Inorg. Chem., 19, 3159 (1980) to produce(2,7,7,12-tetramethyl-3,11-bis(α-methoxybenzylidine)-1,5,9,13-tetraazacyclohexadeca-1,4,9,12-tetraene)nickel(II),the compound of Formula VI in which R₁ is hydrogen, R₂ is methyl and R₃is phenyl.

Next, the methoxyl groups of the product were replaced by methylaminogroups in the manner described in the aforementioned Schammel paper andalso described above, thereby producing the corresponding compound ofFormula VII in which R' is hydrogen and R" is methyl, namely(2,7,7,12-tetramethyl-3,11-bis(α-methylaminobenzylidine)-1,5,9,13-tetraazacyclohexadeca-1,4,9,12-tetraene)nickel(II)hexafluorophosphate. This compound was then reacted with acetonitrileand sodium methoxide in methanol and then with the appropriate dibromideto introduce an m-xylylene bridge R, as described in Busch et al,J.A.C.S. 103, 1472 (1981), thereby producing the final product, compound194.

METHOD U

Example IV above was repeated except that stearoyl chloride wassubstituted for benzoyl chloride, thereby producing a compound analogousto the compound of Formula XV but having n-heptadecyl groups in place ofthe phenyl groups. 4 g. (3.5 mmole) of the resultant compound wasdissolved in 100 ml. of acetonitrile and slowly dripped into a solutionof 3.0 g. (35 mmole) of piperazine in 100 ml. of methanol. The resultantsolution was concentrated to an oil on a rotary evaporator, ethanol wasadded and the solution was placed in a freezer overnight. The solutionwas then filtered to remove an oily precipitate and the filtratereturned to the freezer. Yellow microcrystals precipitated and werecollected, washed with a small amount of ethanol, and air dried toproduce 0.85 g. of product (19.4% based upon the heptadecyl compound).Alternatively, the product could be isolated by removing the solventfrom the reaction mixture on a rotary evaporator, adding ethanol to theresidue and very slowly evaporating the solvent without heat. 1 g. (0.79mmole) of the yellow product was dissolved in 125 ml. of acetonitrileand 0.20 g. (0.87 mmole) of 3,6-bis(chloromethyl)durene was dissolvedseparately in 125 ml. of acetonitrile. The two solutions were drippedsimultaneously into a reservoir of 100 ml. of refluxing acetonitrile andthe resulting solution was gently refluxed overnight. Heating wasdiscontinued, 0.5 ml. (3.6 mmole) of triethylamine was added and thesolution was concentrated to 10 ml. on a rotary evaporator. The liquidresidue was applied to an alumina and eluted with acetonitrile, thefastest moving yellow band being collected and then concentrated to anoil on a rotary evaporator. Ethanol was added to yield an orange powderwhich was recrystallized from acetonitrile/ethanol to yield orangeplate-like crystals of the final product,2,17-di(n-heptadecyl)-9,10,19,25,33,34-hexamethyl-3,6,13,16,20,24,27,31-octaazapentacyclo[16.7.7.2⁸,11.2³,6.2¹³,16]octatriaconta-1,8,10,17,19,24,26,31,33-nonaene-κ⁴ N)nickel(II)]hexafluorophosphate.

METHOD V

This is essentially a variant of Method U above. To produce aoctamethylene group R₃, sebacoyl chloride was substituted for stearoyland the intermediate piperazine product was isolated by reducing thereaction mixture to dryness and slurrying the residue twice with ethanoland once with water to remove the excess piperazine. The remaining solidwas filtered, air-dried and used for the subsequent bridging reaction toinsert the bis(piperazino) bridge. The second reaction was carried outexactly as in Method U. The structure of the product (compound 198) wasconfirmed by a complete X-ray structure determination.

                                      TABLE 7                                     __________________________________________________________________________    Cmpd.                                                                             Synthetic                                                                             Analysis (Calculated)                                                                     Analysis (Found)                                      No. Method  % C                                                                              % H                                                                              % N                                                                              % M                                                                              % C                                                                              % H                                                                              % N                                                                              % M                                                                              Formula                                   __________________________________________________________________________    1(c)                                                                              A       36.97                                                                            5.13                                                                             11.25                                                                            7.86                                                                             36.84                                                                            5.21                                                                             11.14                                                                            7.98                                                                             [NiC.sub.23 H.sub.38 N.sub.6 ](PF.sub.                                        6).sub.2                                  2(c)                                                                              D       38.08                                                                            5.24                                                                             12.43                                                                            7.47                                                                             37.99                                                                            5.13                                                                             12.34                                                                            7.48                                                                             [CoC.sub.25 H.sub.41 N.sub.7 ](PF.sub.                                        6).sub.2                                  3(c)                                                                              E       44.23                                                                            6.10                                                                             14.23                                                                            8.38                                                                             44.03                                                                            6.20                                                                             14.31                                                                            8.25                                                                             [FeC.sub.23 H.sub.38 N.sub.6 Cl]PF.sub                                        .6                                        4   B       36.04                                                                            4.95                                                                             11.46                                                                            -- 36.09                                                                            5.18                                                                             11.41                                                                            -- [NiC.sub.22 H.sub.36 N.sub.6 ](PF.sub.                                        6).sub.2                                  5   E       42.56                                                                            5.85                                                                             13.54                                                                            8.99                                                                             42.61                                                                            5.87                                                                             13.65                                                                            8.76                                                                             [FeC.sub.22 H.sub.36 N.sub.6 Cl]PF.sub                                        .6                                        6   A       37.87                                                                            5.30                                                                             11.04                                                                            7.71                                                                             38.11                                                                            5.41                                                                             11.02                                                                            7.55                                                                             [NiC.sub.24 H.sub.40 N.sub.6 ](PF.sub.                                        6).sub.2                                  7   D/Ex. X 37.86                                                                            5.30                                                                             11.04                                                                            -- 38.16                                                                            5.47                                                                             11.17                                                                            -- [CoC.sub.24 H.sub.40 N.sub.6 ](PF.sub.                                        6).sub.2                                  8   E       44.41                                                                            6.17                                                                             12.95                                                                            8.64                                                                             44.30                                                                            6.09                                                                             12.90                                                                            8.72                                                                             [FeC.sub.24 H.sub.40 N.sub.6 Cl]PF.sub                                        .6                                        9   A       44.83                                                                            4.70                                                                             9.80                                                                             6.85                                                                             44.95                                                                            4.83                                                                             9.93                                                                             6.56                                                                             [NiC.sub.32 H.sub.40 N.sub.6 ](PF.sub.                                        6).sub.2                                  10  D       45.77                                                                            5.23                                                                             10.38                                                                            6.24                                                                             45.63                                                                            5.37                                                                             10.28                                                                            6.09                                                                             [CoC.sub.36 H.sub.49 N.sub.7 O](PF.sub                                        .6).sub.2                                 11  A       46.12                                                                            5.01                                                                             9.49                                                                             6.63                                                                             46.07                                                                            5.20                                                                             9.60                                                                             6.47                                                                             [NiC.sub.26 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  12  D       46.11                                                                            5.01                                                                             9.50                                                                             6.68                                                                             46.11                                                                            5.19                                                                             9.63                                                                             6.45                                                                             [CoC.sub.34 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  13  E       52.83                                                                            5.47                                                                             10.87                                                                            7.22                                                                             52.60                                                                            5.74                                                                             10.68                                                                            7.32                                                                             [FeC.sub.34 H.sub.44 N.sub.6 Cl]PF.sub                                        .6                                        14  G       42.66                                                                            6.32                                                                             12.44                                                                            9.41                                                                             42.62                                                                            6.81                                                                             12.15                                                                            8.98                                                                             [CuC.sub.24 H.sub.40 N.sub.6 Cl]PF.sub                                        .6                                        15  A       41.15                                                                            5.92                                                                             10.28                                                                            -- 41.14                                                                            6.14                                                                             10.36                                                                            -- [NiC.sub.28 H.sub.48 N.sub.6 ](PF.sub.                                        6).sub.2                                  16  B       36.97                                                                            5.13                                                                             11.25                                                                            -- 37.35                                                                            5.34                                                                             11.46                                                                            -- [NiC.sub.23 H.sub. 38 N.sub.6                                                 ](PF.sub.6).sub.2                         17  D       36.96                                                                            5.12                                                                             11.24                                                                            7.88                                                                             36.79                                                                            5.13                                                                             11.21                                                                            7.62                                                                             [CoC.sub.23 H.sub.38 N.sub.6 ](PF.sub.                                        6).sub.2                                  18  E       51.25                                                                            7.11                                                                             15.59                                                                            -- 51.27                                                                            7.13                                                                             15.65                                                                            -- [FeC.sub.23 H.sub.38 N.sub.6 Cl]Cl        19  N       40.78                                                                            5.36                                                                             11.10                                                                            -- 40.82                                                                            5.45                                                                             11.10                                                                            -- [FeC.sub.29 H.sub.43 N.sub.7 O](PF.sub                                        .6).sub.2                                 20  C/Ex. V 38.73                                                                            5.46                                                                             10.84                                                                            -- 38.51                                                                            5.71                                                                             10.74                                                                            -- [NiC.sub.25 H.sub.42 N.sub.6 ](PF.sub.                                        6).sub.2                                  21  D       38.72                                                                            5.46                                                                             10.84                                                                            7.60                                                                             38.67                                                                            5.66                                                                             10.64                                                                            7.49                                                                             [CoC.sub.25 H.sub.42 N.sub.6 ](PF.sub.                                        6).sub.2                                  22  E       45.28                                                                            6.34                                                                             12.68                                                                            8.45                                                                             45.56                                                                            6.51                                                                             12.90                                                                            8.22                                                                             [FeC.sub.25 H.sub.42 N.sub.6 Cl]PF.sub                                        .6                                        23  H       43.43                                                                            5.67                                                                             15.01                                                                            -- 43.39                                                                            5.70                                                                             14.96                                                                            -- [CoC.sub.27 H.sub.42 N.sub.8 S.sub.2                                          ]PF.sub.6                                 24  B       45.49                                                                            4.86                                                                             9.64                                                                             -- 45.79                                                                            5.06                                                                             9.59                                                                             -- [NiC.sub.33 H.sub.42 N.sub.6 ](PF.sub.                                        6).sub.2                                  25  D       45.48                                                                            4.86                                                                             9.64                                                                             6.76                                                                             45.20                                                                            5.06                                                                             9.87                                                                             6.58                                                                             [CoC.sub.33 H.sub.42 N.sub.6 ](PF.sub.                                        6).sub.2                                  26  C       45.14                                                                            5.07                                                                             9.32                                                                             -- 45.14                                                                            5.07                                                                             9.27                                                                             -- [NiC.sub.35 H.sub.46 N.sub.6 ](PF.sub.                                        6).sub.2                                  27  D       44.77                                                                            5.00                                                                             9.29                                                                             6.27                                                                             44.78                                                                            5.56                                                                             8.92                                                                             6.04                                                                             [CoC.sub.35 H.sub.46 N.sub.6 ](PF.sub.                                        6).sub.2                                  28  E       53.41                                                                            5.89                                                                             10.68                                                                            7.10                                                                             53.36                                                                            5.89                                                                             10.78                                                                            7.33                                                                             [FeC.sub.35 H.sub.46 N.sub.6 Cl]PF.sub                                        .6                                        29  B       41.90                                                                            6.06                                                                             10.11                                                                            -- 42.28                                                                            6.21                                                                             10.18                                                                            -- [NiC.sub.29 H.sub.50 N.sub.6 ](PF.sub.                                        6).sub.2                                  30  D       43.14                                                                            6.49                                                                             10.67                                                                            6.41                                                                             43.44                                                                            6.50                                                                             10.96                                                                            6.45                                                                             [CoC.sub.33 H.sub.59 N.sub.7 O](PF.sub                                        .6).sub.2                                 31  A/Ex. I 38.68                                                                            5.74                                                                             10.41                                                                            -- 38.64                                                                            5.72                                                                             10.53                                                                            -- [NiC.sub.24 H.sub.40 N.sub.6 ](PF.sub.                                        6).sub.2                                                                      (contains one C.sub.2 H.sub.5 OH          32  D       37.86                                                                            5.30                                                                             11.04                                                                            -- 37.77                                                                            5.32                                                                             11.48                                                                            -- [CoC.sub.24 H.sub.40 N.sub.6 ](PF.sub.                                        6).sub.2                                  33  E       44.42                                                                            6.21                                                                             12.95                                                                            8.61                                                                             44.38                                                                            5.93                                                                             12.66                                                                            8.89                                                                             [FeC.sub.24 H.sub.40 N.sub.6 Cl]PF.sub                                        .6                                        34  N       41.48                                                                            5.50                                                                             10.92                                                                            -- 41.59                                                                            5.66                                                                             10.87                                                                            -- [FeC.sub.30 H.sub.45 N.sub.7 O](PF.sub                                        .6).sub.2                                 35  G       38.45                                                                            5.71                                                                             10.35                                                                            7.82                                                                             38.38                                                                            5.89                                                                             10.40                                                                            7.61                                                                             [CuC.sub.26 H.sub.46 N.sub.6 O](PF.sub                                        .6).sub.2                                 36  A       39.56                                                                            5.62                                                                             10.65                                                                            -- 39.46                                                                            5.53                                                                             10.60                                                                            -- [NiC.sub.26 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  37  R       53.08                                                                            7.88                                                                             14.29                                                                            -- 53.10                                                                            8.14                                                                             14.38                                                                            -- [NiC.sub.26 H.sub.44 N.sub.6 ]Cl.sub.2                                        r                                         38  D       39.55                                                                            5.62                                                                             10.64                                                                            7.46                                                                             39.53                                                                            5.70                                                                             10.76                                                                            7.43                                                                             [CoC.sub.26 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  39  I/Ex. XI                                                                              41.34                                                                            5.78                                                                             12.86                                                                            -- 41.44                                                                            6.08                                                                             12.91                                                                            -- [CoC.sub.30 H.sub.50 N.sub.8 ](PF.sub.                                        6).sub.2                                  40  I       40.61                                                                            5.64                                                                             13.07                                                                            -- 40.87                                                                            5.83                                                                             13.06                                                                            -- [CoC.sub.29 H.sub.48 N.sub.8 ](PF.sub.                                        6).sub.2                                  41  I       42.86                                                                            5.69                                                                             11.29                                                                            -- 42.99                                                                            5.60                                                                             11.40                                                                            -- [CoC.sub.31 H.sub.49 N.sub.7 ](PF.sub.                                        6).sub.2                                  42  I       46.15                                                                            6.31                                                                             13.95                                                                            -- 45.90                                                                            6.44                                                                             13.64                                                                            -- [CoC.sub.27 H.sub.44 N.sub.7 S]PF.sub.                                        6                                         43  H       44.20                                                                            5.82                                                                             14.71                                                                            7.75                                                                             44.35                                                                            5.90                                                                             14.80                                                                            7.61                                                                             [CoC.sub.28 H.sub.44 N.sub.8 S.sub.2                                          ]PF.sub.6                                 44  H       46.16                                                                            6.09                                                                             15.38                                                                            -- 45.88                                                                            6.01                                                                             15.02                                                                            -- [CoC.sub.28 H.sub.44 N.sub.8 O.sub.2                                          ]PF.sub.6                                 45  H       42.86                                                                            6.09                                                                             23.07                                                                            -- 42.51                                                                            6.39                                                                             22.50                                                                            -- [CoC.sub.26 H.sub.44 N.sub.12                                                 ]PF.sub.6                                 46  E       46.13                                                                            6.55                                                                             12.41                                                                            -- 45.93                                                                            6.77                                                                             12.24                                                                            -- [FeC.sub.26 H.sub.44 N.sub.6 Cl]PF.sub                                        .6                                        47  N       41.20                                                                            5.59                                                                             12.08                                                                            -- 40.97                                                                            5.66                                                                             12.25                                                                            -- [FeC.sub.29 H.sub.47 N.sub.7 O](PF.sub                                        .6).sub.2                                 48  N       43.01                                                                            5.53                                                                             10.97                                                                            6.25                                                                             41.91                                                                            5.73                                                                             11.29                                                                            5.90                                                                             [FeC.sub.32 H.sub.49 N.sub.7 O](PF.sub                                        .6).sub.2                                 49  N       41.53                                                                            5.62                                                                             12.50                                                                            6.23                                                                             41.80                                                                            5.68                                                                             12.98                                                                            5.78                                                                             [FeC.sub.31 H.sub.50 N.sub.8 O](PF.sub                                        .6).sub.2                                 50  J/Ex. XV                                                                              37.99                                                                            5.40                                                                             10.23                                                                            6.80                                                                             37.99                                                                            5.11                                                                             10.24                                                                            7.03                                                                             [FeC.sub.26 H.sub.44 N.sub.6 Cl](PF.su                                        b.6).sub.2                                51  L       45.80                                                                            6.83                                                                             11.87                                                                            -- 45.55                                                                            6.63                                                                             12.12                                                                            -- [MnC.sub.26 H.sub.44 N.sub.6 Cl]PF.sub                                        .6                                        52  K/Ex. XIX                                                                             38.00                                                                            5.36                                                                             10.23                                                                            6.69                                                                             38.21                                                                            5.51                                                                             10.21                                                                            6.50                                                                             [MnC.sub.26 H.sub.44 N.sub.6 Cl](PF.su                                        b.6).sub.2                                53  G/Ex. XVII                                                                            39.32                                                                            5.58                                                                             10.58                                                                            8.00                                                                             39.42                                                                            5.49                                                                             10.49                                                                            7.95                                                                             [CuC.sub.26 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  54  A/Ex. IV                                                                              46.12                                                                            5.01                                                                             9.49                                                                             6.63                                                                             45.97                                                                            5.14                                                                             9.36                                                                             6.37                                                                             [NiC.sub.34 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  55  D       46.11                                                                            5.01                                                                             9.49                                                                             6.65                                                                             45.83                                                                            5.20                                                                             9.26                                                                             6.52                                                                             [CoC.sub.34 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  56  A       47.34                                                                            5.30                                                                             9.20                                                                             -- 47.38                                                                            5.35                                                                             9.11                                                                             -- [NiC.sub.36 H.sub.48 N.sub.6 ](PF.sub.                                        6).sub.2                                  57  D       47.33                                                                            5.30                                                                             9.20                                                                             6.45                                                                             47.29                                                                            5.40                                                                             9.01                                                                             6.28                                                                             [CoC.sub.36 H.sub.48 N.sub.6 ](PF.sub.                                        6).sub.2                                  58  E       53.00                                                                            6.43                                                                             9.87                                                                             6.56                                                                             52.70                                                                            6.21                                                                             10.10                                                                            6.71                                                                             [FeC.sub.36 H.sub.48 N.sub.6 Cl]PF.sub                                        .6                                        59  E       60.48                                                                            5.92                                                                             8.82                                                                             5.86                                                                             60.56                                                                            6.02                                                                             8.84                                                                             6.12                                                                             [FeC.sub.48 H.sub.56 N.sub.6 Cl]PF.sub                                        .6                                        60  A       42.62                                                                            6.20                                                                             9.94                                                                             6.94                                                                             42.79                                                                            6.40                                                                             10.00                                                                            6.73                                                                             [NiC.sub.30 H.sub.52 N.sub.6 ](PF.sub.                                        6).sub.2                                  61  D       42.61                                                                            6.20                                                                             9.94                                                                             6.97                                                                             42.67                                                                            6.34                                                                             9.98                                                                             6.84                                                                             [CoC.sub.30 H.sub.52 N.sub.6 ](PF.sub.                                        6).sub.2                                  62  A       46.52                                                                            6.94                                                                             9.04                                                                             6.25                                                                             46.60                                                                            7.09                                                                             9.15                                                                             6.17                                                                             [NiC.sub.36 H.sub.60 N.sub.6 ](PF.sub.                                        6).sub.2                                  63  A       38.92                                                                            5.40                                                                             12.22                                                                            -- 38.73                                                                            5.58                                                                             12.00                                                                            -- [NiC.sub.26 H.sub.43 N.sub.7 ](PF.sub.                                        6).sub.2                                  64  D       38.91                                                                            5.40                                                                             12.22                                                                            7.34                                                                             39.00                                                                            5.72                                                                             11.94                                                                            7.40                                                                             [CoC.sub.26 H.sub.43 N.sub.7 ](PF.sub.                                        6).sub.2                                  65(c)                                                                             P       41.25                                                                            5.69                                                                             10.31                                                                            -- 41.23                                                                            6.19                                                                             10.41                                                                            -- [NiC.sub.28 H.sub.46 N.sub.6 ](PF.sub.                                        6).sub.2                                  66  P       42.00                                                                            5.83                                                                             10.13                                                                            -- 41.91                                                                            5.86                                                                             10.09                                                                            -- [NiC.sub.29 H.sub.48 N.sub.6 ](PF.sub.                                        6).sub.2                                  67  P       42.72                                                                            5.98                                                                             9.96                                                                             -- 42.99                                                                            6.00                                                                             9.91                                                                             -- [NiC.sub.30 H.sub.50 N.sub.6 ](PF.sub.                                        6).sub.2                                  68  B       39.24                                                                            5.51                                                                             11.44                                                                            -- 38.97                                                                            5.62                                                                             11.50                                                                            -- [NiC.sub.26 H.sub.43.5 N.sub.6.5                                              ](PF.sub.6).sub.2                         69  D       40.62                                                                            5.64                                                                             13.07                                                                            6.87                                                                             40.61                                                                            5.79                                                                             13.01                                                                            7.25                                                                             [CoC.sub.29 H.sub.48 N.sub.8 ](PF.sub.                                        6).sub.2                                  70  C       40.37                                                                            5.77                                                                             10.46                                                                            -- 40.07                                                                            6.10                                                                             10.52                                                                            -- [NiC.sub.27 H.sub.46 N.sub.6 ](PF.sub.                                        6).sub.2                                  71  D       40.36                                                                            5.77                                                                             10.46                                                                            7.33                                                                             40.53                                                                            5.96                                                                             10.60                                                                            7.11                                                                             [CoC.sub.27 H.sub.46 N.sub.6 ](PF.sub.                                        6).sub.2                                  72  H       44.90                                                                            6.00                                                                             14.48                                                                            -- 44.50                                                                            5.92                                                                             13.50                                                                            -- [CoC.sub.29 H.sub.46 N.sub.8 S.sub.2                                          ]PF.sub.6                                 73  B       46.74                                                                            5.16                                                                             9.34                                                                             6.53                                                                             46.78                                                                            5.38                                                                             9.41                                                                             6.27                                                                             [NiC.sub.35 H.sub.46 N.sub.6 ](PF.sub.                                        6).sub.2                                  74  D       46.73                                                                            5.15                                                                             9.34                                                                             6.55                                                                             46.54                                                                            5.19                                                                             9.25                                                                             6.55                                                                             [CoC.sub.35 H.sub.46 N.sub.6 ](PF.sub.                                        6).sub.2                                  75  C       47.92                                                                            5.43                                                                             9.06                                                                             -- 47.75                                                                            5.58                                                                             8.91                                                                             -- [NiC.sub.37 H.sub.50 N.sub.6 ](PF.sub.                                        6).sub.2                                  76  D       47.90                                                                            5.43                                                                             9.06                                                                             6.35                                                                             47.51                                                                            5.53                                                                             9.23                                                                             6.04                                                                             [CoC.sub.37 H.sub.50 N.sub.6 ](PF.sub.                                        6).sub.2                                  77  B       43.68                                                                            6.36                                                                             10.35                                                                            -- 43.73                                                                            6.50                                                                             10.17                                                                            -- [NiC.sub.31 H.sub.54 N.sub.6 ](PF.sub.                                        6).sub.2                                  78  D       43.31                                                                            6.33                                                                             9.78                                                                             6.85                                                                             43.53                                                                            6.42                                                                             10.03                                                                            6.54                                                                             [CoC.sub.31 H.sub.54 N.sub.6 ](PF.sub.                                        6).sub.2                                  79  P/Ex. VII                                                                             43.42                                                                            6.11                                                                             9.80                                                                             6.84                                                                             43.62                                                                            6.24                                                                             9.86                                                                             6.62                                                                             [NiC.sub.31 H.sub.52 N.sub.6 ](PF.sub.                                        6).sub.2                                  80  B       40.04                                                                            5.66                                                                             11.24                                                                            -- 40.31                                                                            5.97                                                                             11.05                                                                            -- [NiC.sub.26 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  81  D       39.55                                                                            5.62                                                                             10.64                                                                            7.46                                                                             39.81                                                                            5.69                                                                             10.59                                                                            7.56                                                                             [CoC.sub.26 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  82  C       41.15                                                                            5.92                                                                             10.28                                                                            -- 41.08                                                                            5.98                                                                             10.16                                                                            -- [NiC.sub.28 H.sub.48 N.sub.6 ](PF.sub.                                        6).sub.2                                  83  D       41.00                                                                            6.17                                                                             9.89                                                                             6.94                                                                             40.69                                                                            6.11                                                                             9.87                                                                             6.94                                                                             [CoC.sub.29 H.sub.52 N.sub.6 ](PF.sub.                                        6).sub.2                                  84  B       47.34                                                                            5.30                                                                             9.20                                                                             -- 47.12                                                                            5.45                                                                             9.08                                                                             -- [NiC.sub.36 H.sub.48 N.sub.6 ](PF.sub.                                        6).sub.2                                  85  D       48.47                                                                            5.57                                                                             8.92                                                                             6.26                                                                             48.36                                                                            5.47                                                                             8.73                                                                             6.07                                                                             [CoC.sub.38 H.sub.52 N.sub.6 ](PF.sub.                                        6).sub.2                                  86  B       39.97                                                                            4.64                                                                             10.76                                                                            -- 40.29                                                                            4.84                                                                             10.84                                                                            -- [NiC.sub.26 H.sub.36 N.sub.6 ](PF.sub.                                        6).sub.2                                  87  D       40.89                                                                            4.78                                                                             11.92                                                                            7.16                                                                             41.17                                                                            5.00                                                                             11.96                                                                            7.24                                                                             [CoC.sub.28 H.sub.39 N.sub.7 ](PF.sub.                                        6).sub.2                                  88  F/Ex. XIII                                                                            46.69                                                                            5.43                                                                             12.56                                                                            -- 46.53                                                                            5.48                                                                             12.57                                                                            -- [FeC.sub.26 H.sub.36 N.sub.6 Cl]PF.sub                                        .6                                        89  N       43.41                                                                            4.67                                                                             11.07                                                                            6.31                                                                             42.83                                                                            4.93                                                                             10.72                                                                            5.80                                                                             [FeC.sub.32 H.sub.41 N.sub.7 O](PF.sub                                        .6).sub.2                                 90  N       41.91                                                                            4.76                                                                             12.61                                                                            6.29                                                                             40.99                                                                            4.85                                                                             12.64                                                                            5.61                                                                             [FeC.sub.31 H.sub.42 N.sub.8 O](PF.sub                                        .6).sub.2                                 91  N       41.21                                                                            4.61                                                                             12.81                                                                            -- 41.33                                                                            4.84                                                                             12.36                                                                            -- [FeC.sub.30 H.sub.40 N.sub.8 O](PF.sub                                        .6).sub.2                                 92  N       42.68                                                                            4.70                                                                             12.44                                                                            6.20                                                                             42.57                                                                            4.70                                                                             12.57                                                                            6.14                                                                             [FeC.sub.32 H.sub.42 N.sub.8 O](PF.sub                                        .6).sub.2                                 93  C/Ex. III                                                                             41.55                                                                            4.98                                                                             10.38                                                                            -- 41.48                                                                            5.02                                                                             10.40                                                                            -- [NiC.sub.28 H.sub.40 N.sub.6 ](PF.sub.                                        6).sub.2                                  94  D       40.64                                                                            5.11                                                                             10.15                                                                            7.12                                                                             40.97                                                                            5.40                                                                             9.91                                                                             6.93                                                                             [CoC.sub.28 H.sub.42 N.sub.6 O](PF.sub                                        .6 ).sub.2                                95  F/Ex. XIV                                                                             48.26                                                                            5.78                                                                             12.06                                                                            -- 48.22                                                                            5.93                                                                             12.00                                                                            -- [FeC.sub.28 H.sub.40 N.sub.6 Cl]PF.sub                                        .6                                        96  N       43.24                                                                            5.06                                                                             112.23                                                                           -- 43.76                                                                            5.01                                                                             12.92                                                                            -- [FeC.sub.33 H.sub.46 N.sub.8 O](PF.sub                                        .6).sub.2                                 97  N       42.53                                                                            4.95                                                                             11.20                                                                            -- 43.20                                                                            5.33                                                                             12.24                                                                            -- [FeC.sub.31 H.sub.43 N.sub.7 O](PF.sub                                        .6).sub.2                                 98  N       42.59                                                                            4.91                                                                             12.42                                                                            6.19                                                                             41.37                                                                            5.08                                                                             12.37                                                                            5.90                                                                             [FeC.sub.32 H.sub.44 N.sub.8 O](PF.sub                                        .6).sub.2                                 99  N       43.98                                                                            4.99                                                                             12.07                                                                            6.01                                                                             43.51                                                                            5.27                                                                             12.70                                                                            5.89                                                                             [FeC.sub.34 H.sub.46 N.sub.8 O](PF.sub                                        .6).sub.2                                 100 J       39.95                                                                            4.79                                                                             9.98                                                                             6.63                                                                             39.99                                                                            4.91                                                                             10.03                                                                            6.95                                                                             [FeC.sub.28 H.sub.40 N.sub.6 Cl](PF.su                                        b.6).sub.2                                101 L       41.75                                                                            5.01                                                                             10.43                                                                            6.82                                                                             41.96                                                                            5.32                                                                             10.67                                                                            6.63                                                                             [MnC.sub.28 H.sub.40 N.sub.6 ](PF.sub.                                        6).sub.2                                  102 K       39.99                                                                            4.80                                                                             9.99                                                                             6.52                                                                             39.99                                                                            4.97                                                                             10.12                                                                            6.26                                                                             [MnC.sub.28 H.sub.40 N.sub.6 Cl](PF.su                                        b.6).sub.2                                103 G/Ex. XVIII                                                                           42.13                                                                            5.07                                                                             11.47                                                                            7.43                                                                             42.10                                                                            5.10                                                                             11.22                                                                            7.37                                                                             [CuC.sub.30 H.sub.43 N.sub. 7                                                 ](PF.sub.6).sub.2                         104 C       45.71                                                                            5.87                                                                             9.41                                                                             -- 45.05                                                                            5.97                                                                             9.22                                                                             -- [NiC.sub.34 H.sub.52 N.sub.6 ](PF.sub.                                        6).sub.2                                  105 C       36.71                                                                            4.62                                                                             14.27                                                                            7.48                                                                             36.79                                                                            4.85                                                                             14.21                                                                            7.29                                                                             [NiC.sub.32 H.sub.42 N.sub.8 ](PF.sub.                                        6).sub.2                                  106 C       49.97                                                                            5.03                                                                             8.74                                                                             -- 49.63                                                                            5.29                                                                             8.71                                                                             -- [NiC.sub.40 H.sub.48 N.sub.6 ](PF.sub.                                        6).sub.2                                  107 E       50.46                                                                            5.14                                                                             9.81                                                                             5.59                                                                             50.44                                                                            5.16                                                                             9.39                                                                             5.72                                                                             [FeC.sub.42 H.sub.51 N.sub.7 ](PF.sub.                                        6).sub.2                                  108 A       40.60                                                                            4.50                                                                             11.40                                                                            -- 40.56                                                                            4.90                                                                             11.40                                                                            -- [NiC.sub.26 H.sub.34 N.sub.6 ](PF.sub.                                        6).sub.2                                  109 B       48.07                                                                            6.37                                                                             8.85                                                                             6.19                                                                             48.14                                                                            6.56                                                                             8.91                                                                             6.32                                                                             [NiC.sub.38 H.sub.58 N.sub.6 ](PF.sub.                                        6).sub.2                                  110 C       49.14                                                                            6.55                                                                             8.60                                                                             -- 49.40                                                                            6.88                                                                             8.59                                                                             -- [NiC.sub.40 H.sub.62 N.sub.6 ](PF.sub.                                        6).sub.2                                  111 E       53.96                                                                            7.31                                                                             9.44                                                                             -- 53.81                                                                            7.38                                                                             9.69                                                                             -- [FeC.sub.40 H.sub.62 N.sub.6 Cl](PF.su                                        b.6)                                                                          .1.5H.sub.2 O                             112 B       47.76                                                                            4.45                                                                             9.28                                                                             6.48                                                                             47.65                                                                            4.59                                                                             9.28                                                                             6.29                                                                             [NiC.sub.36 H.sub.40 N.sub.6 ](PF.sub.                                        6).sub.2                                  113 D       48.21                                                                            4.58                                                                             10.36                                                                            6.22                                                                             48.24                                                                            4.60                                                                             10.26                                                                            6.18                                                                             [CoC.sub.38 H.sub.43 N.sub.7 ](PF.sub.                                        6).sub.2                                  114 C       48.90                                                                            4.75                                                                             9.00                                                                             -- 48.58                                                                            4.86                                                                             9.21                                                                             -- [NiC.sub.38 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  115 D       48.88                                                                            4.75                                                                             9.00                                                                             6.31                                                                             48.59                                                                            4.80                                                                             8.99                                                                             6.28                                                                             [CoC.sub.38 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  116 E       49.52                                                                            5.10                                                                             9.82                                                                             5.59                                                                             49.27                                                                            4.95                                                                             9.62                                                                             5.60                                                                             [FeC.sub.40 H.sub.47 N.sub.2 ](PF.sub.                                        6).sub.2                                                                      .0.5C.sub.2 H.sub.5 OH                    117 C       55.32                                                                            4.83                                                                             7.74                                                                             5.41                                                                             55.47                                                                            4.89                                                                             7.58                                                                             5.37                                                                             [NiC.sub.50 H.sub.52 N.sub.6 ](PF.sub.                                        6).sub.2                                  118 E       54.41                                                                            5.43                                                                             8.16                                                                             4.65                                                                             54.28                                                                            5.17                                                                             8.26                                                                             4.54                                                                             [FeC.sub.52 H.sub.55 N.sub.7 ](PF.sub.                                        6).sub.2                                                                      .2.5CH.sub.3 0H                           119 E       54.52                                                                            5.49                                                                             9.54                                                                             6.34                                                                             53.81                                                                            5.58                                                                             9.38                                                                             6.19                                                                             [FeC.sub. 40 H.sub.48 N.sub.6                                                 ClO.sub.2 ]PF.sub.6                       120 E       50.76                                                                            4.99                                                                             9.11                                                                             -- 50.20                                                                            5.14                                                                             8.95                                                                             -- [FeC.sub.38 H.sub.42 N.sub.6 Cl.sub.3                                         ]PF.sub.6                                                                     .CH.sub.3 OH                              121 E       49.64                                                                            4.88                                                                             8.91                                                                             8.28                                                                             49.95                                                                            5.06                                                                             9.02                                                                             7.82                                                                             [FeC.sub.38 H.sub.42 N.sub.6 ClF.sub.2                                         ]PF.sub.6                                122 C       47.88                                                                            4.97                                                                             7.98                                                                             -- 47.90                                                                            5.28                                                                             7.81                                                                             -- [NiC.sub.42 H.sub.52 N.sub.6 O.sub.4                                          ](PF.sub.6).sub.2                         123 P       44.90                                                                            5.76                                                                             9.24                                                                             -- 45.31                                                                            5.87                                                                             9.60                                                                             -- [NiC.sub.32 H.sub.46 N.sub.6 ](PF.sub.                                        6).sub.2                                  124 P       43.84                                                                            5.22                                                                             9.89                                                                             -- 44.19                                                                            4.78                                                                             9.99                                                                             -- [NiC.sub.31 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  125 B       39.97                                                                            4.64                                                                             10.76                                                                            -- 40.15                                                                            4.50                                                                             10.96                                                                            -- [NiC.sub.26 H.sub.36 N.sub.6 ](PF.sub.                                        6).sub.2                                  126 F       46.69                                                                            5.43                                                                             12.56                                                                            -- 46.59                                                                            5.77                                                                             11.93                                                                            -- [FeC.sub.26 H.sub.36 N.sub.6 Cl]PF.sub                                        .6                                        127 N       41.10                                                                            4.64                                                                             11.57                                                                            -- 40.05                                                                            4.97                                                                             11.01                                                                            -- [FeC.sub.29 H.sub.39 N.sub.7 O](PF.sub                                        .6).sub.2                                 128 N       43.41                                                                            4.67                                                                             11.07                                                                            -- 43.07                                                                            4.76                                                                             11.09                                                                            -- [FeC.sub.32 H.sub.41 N.sub.7 O](PF.sub                                        .6).sub.2                                 129 N       41.91                                                                            4.76                                                                             12.61                                                                            -- 41.50                                                                            5.12                                                                             12.57                                                                            -- [FeC.sub.31 H.sub.42 N.sub.8 O](PF.sub                                        .6).sub.2                                 130 C       41.56                                                                            4.98                                                                             10.38                                                                            -- 41.90                                                                            5.37                                                                             10.18                                                                            -- [NiC.sub.28 H.sub.40 N.sub.6 ](PF.sub.                                        6).sub.2                                  131 B/Ex. II                                                                              48.02                                                                            5.32                                                                             9.08                                                                             -- 48.36                                                                            5.36                                                                             9.14                                                                             -- [NiC.sub.37 H.sub.48 N.sub.6 ](PF.sub.                                        6).sub.2                                  132 F       63.16                                                                            6.88                                                                             11.94                                                                            7.94                                                                             62.90                                                                            6.87                                                                             12.16                                                                            7.64                                                                             [FeC.sub.3 H.sub.48 N.sub.6 Cl]Cl         133 N       49.77                                                                            5.41                                                                             9.23                                                                             5.26                                                                             49.72                                                                            5.43                                                                             9.65                                                                             5.11                                                                             [FeC.sub.43 H.sub.53 N.sub.7 O](PF.sub                                        .6).sub.2                                 134 N       48.50                                                                            5.49                                                                             10.52                                                                            5.25                                                                             48.61                                                                            5.48                                                                             10.59                                                                            5.14                                                                             [FeC.sub.42 H.sub.54 N.sub.8 O](PF.sub                                        .6).sub.2                                 135 B       37.28                                                                            4.97                                                                             10.44                                                                            -- 37.39                                                                            5.04                                                                             10.37                                                                            -- [NiC.sub.25 H.sub.40 N.sub.6 O.sub.2                                          ](PF.sub.6).sub.2                         136 B       39.18                                                                            5.32                                                                             10.57                                                                            -- 39.64                                                                            5.34                                                                             10.69                                                                            -- [NiC.sub.26 H.sub.42 N.sub.6 ](PF.sub.                                        6).sub.2                                  137 C       47.92                                                                            5.40                                                                             9.07                                                                             -- 47.89                                                                            5.40                                                                             9.06                                                                             -- [NiC.sub.37 H.sub.50 N.sub.6 ](PF.sub.                                        6).sub.2                                  138 C       41.50                                                                            5.04                                                                             10.01                                                                            6.99                                                                             41.28                                                                            5.19                                                                             9.98                                                                             6.73                                                                             [NiC.sub.29 H.sub.42 N.sub.6 O](PF.sub                                        .6).sub.2                                 139 B       32.98                                                                            5.03                                                                             10.49                                                                            7.33                                                                             33.13                                                                            5.01                                                                             10.55                                                                            7.43                                                                             [NiC.sub.22 H.sub.36 N.sub.6 S](PF.sub                                        .6).sub.2                                 140 B       34.65                                                                            5.06                                                                             10.54                                                                            7.36                                                                             34.72                                                                            5.23                                                                             10.53                                                                            7.22                                                                             [NiC.sub.23 H.sub.38 N.sub.6 S](PF.sub                                        .6).sub.2                                 141 C       41.54                                                                            4.88                                                                             9.69                                                                             -- 41.05                                                                            4.51                                                                             9.62                                                                             -- [NiC.sub.30 H.sub.44 N.sub.6 O.sub.2                                          ](PF.sub.6).sub.2                         142 C       38.19                                                                            5.00                                                                             12.47                                                                            7.47                                                                             38.38                                                                            4.98                                                                             12.22                                                                            7.20                                                                             [NiC.sub.27 H.sub.41 N.sub.7 ](PF.sub.                                        6).sub.2                                  143 A       37.13                                                                            5.32                                                                             12.63                                                                            -- 37.29                                                                            5.45                                                                             12.46                                                                            -- [NiC.sub.24 H.sub.41 N.sub.7 ](PF.sub.                                        6).sub.2                                  144 A       37.99                                                                            5.48                                                                             12.41                                                                            -- 38.09                                                                            5.65                                                                             12.20                                                                            -- [NiC.sub.25 H.sub.43 N.sub.7 ](PF.sub.                                        6).sub.2                                  145 D       37.98                                                                            5.48                                                                             12.40                                                                            -- 37.50                                                                            5.40                                                                             12.65                                                                            -- [CoC.sub.25 H.sub.43 N.sub.7 ](PF.sub.                                        6).sub.2                                  146(c)                                                                            M       38.73                                                                            5.46                                                                             10.84                                                                            -- 38.68                                                                            5.63                                                                             10.93                                                                            -- [NiC.sub.25 H.sub.42 N.sub.6 ](PF.sub.                                        6).sub.2                                  147(c)                                                                            D       39.71                                                                            5.55                                                                             12.01                                                                            7.22                                                                             39.81                                                                            5.65                                                                             12.07                                                                            7.10                                                                             [CoC.sub.27 H.sub.45 N.sub.7 ](PF.sub.                                        6).sub.2                                  148(c)                                                                            M       38.92                                                                            5.40                                                                             12.22                                                                            -- 39.18                                                                            5.53                                                                             12.20                                                                            -- [NiC.sub.24 H.sub.40 N.sub.6 ](PF.sub.                                        6).sub.2                                  149(c)                                                                            M       40.50                                                                            5.70                                                                             11.18                                                                            -- 40.49                                                                            5.93                                                                             11.86                                                                            -- [NiC.sub.26 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  150(c)                                                                            D       40.49                                                                            5.70                                                                             11.80                                                                            7.09                                                                             40.26                                                                            5.69                                                                             11.47                                                                            7.18                                                                             [CoC.sub.28 H.sub.47 N.sub.7 ](PF.sub.                                        6).sub.2                                  151 M       38.71                                                                            5.46                                                                             10.84                                                                            -- 38.79                                                                            5.50                                                                             10.82                                                                            -- [NiC.sub.25 H.sub.42 N.sub.6 ](PF.sub.                                        6).sub.2                                  152 D       40.01                                                                            5.60                                                                             10.37                                                                            7.27                                                                             39.81                                                                            5.34                                                                             10.77                                                                            7.24                                                                             [CoC.sub.25 H.sub.42 N.sub.6 ](PF.sub.                                        6).sub.2                                  153 E       45.29                                                                            6.39                                                                             12.68                                                                            8.42                                                                             45.14                                                                            6.12                                                                             12.69                                                                            8.28                                                                             [FeC.sub.25 H.sub.42 N.sub.6 Cl]PF.sub                                        .6                                        154 M       41.90                                                                            6.06                                                                             10.11                                                                            -- 41.86                                                                            6.05                                                                             10.16                                                                            -- [NiC.sub.29 H.sub.50 N.sub.6 ](PF.sub.                                        6).sub.2                                  155 D       42.67                                                                            6.12                                                                             11.24                                                                            6.75                                                                             42.58                                                                            5.85                                                                             11.16                                                                            6.64                                                                             [CoC.sub.31 H.sub.53 N.sub.7 ](PF.sub.                                        6).sub.2                                  156 M       47.92                                                                            5.43                                                                             9.06                                                                             -- 47.71                                                                            5.56                                                                             9.10                                                                             -- [NiC.sub.37 H.sub.50 N.sub.6 ](PF.sub.                                        6).sub.2                                  157 M       40.37                                                                            5.77                                                                             10.46                                                                            -- 40.21                                                                            5.82                                                                             10.37                                                                            -- [NiC.sub.27 H.sub.46 N.sub.6 ](PF.sub.                                        6).sub.2                                  158 D       39.47                                                                            5.89                                                                             10.23                                                                            7.17                                                                             39.40                                                                            6.04                                                                             9.97                                                                             6.87                                                                             [COC.sub.27 H.sub.48 N.sub.6 O](PF.sub                                        .6).sub.2                                 159 E       46.93                                                                            6.71                                                                             12.16                                                                            8.08                                                                             47.02                                                                            6.79                                                                             12.08                                                                            8.23                                                                             [FeC.sub.27 H.sub.48 N.sub.6 Cl]PF.sub                                        .6                                        160 M       39.56                                                                            5.62                                                                             10.65                                                                            -- 39.44                                                                            5.70                                                                             10.57                                                                            -- [NiC.sub.26 H.sub.44 N.sub.6 ](PF.sub.                                        6).sub.2                                  161 M       41.15                                                                            5.92                                                                             10.28                                                                            -- 41.08                                                                            5.98                                                                             10.19                                                                            -- [NiC.sub.28 H.sub.48 N.sub.6 ](PF.sub.                                        6).sub.2                                  162 D       41.96                                                                            5.99                                                                             11.42                                                                            6.86                                                                             42.09                                                                            6.04                                                                             11.45                                                                            6.80                                                                             [CoC.sub.30 H.sub.512 N.sub.7                                                 ](PF.sub.6).sub.2                         163 E       47.70                                                                            6.86                                                                             11.92                                                                            7.92                                                                             46.50                                                                            6.90                                                                             11.52                                                                            8.15                                                                             [FeC.sub.28 H.sub.48 N.sub.6 Cl]PF.sub                                        .6                                        164 C       36.78                                                                            4.68                                                                             9.69                                                                             -- 36.60                                                                            5.00                                                                             9.64                                                                             -- [NiC.sub.31 H.sub.48 N.sub.7 ](PF.sub.                                        6).sub.3                                  165 A       37.44                                                                            4.91                                                                             9.55                                                                             -- 37.30                                                                            4.83                                                                             9.53                                                                             -- [NiC.sub.32 H.sub.50 N.sub.7 ](PF.sub.                                        6).sub.3                                  166 D       37.44                                                                            4.91                                                                             9.55                                                                             5.74                                                                             34.40                                                                            4.86                                                                             9.68                                                                             5.61                                                                             [CoC.sub.32 H.sub.50 N.sub.7 ](PF.sub.                                        6).sub.3                                  167 C       39.03                                                                            4.43                                                                             9.37                                                                             -- 39.11                                                                            4.59                                                                             9.43                                                                             -- [NiC.sub.34 H.sub.46 N.sub.7 ](PF.sub.                                        6).sub.3                                  168 D       42.96                                                                            5.46                                                                             11.31                                                                            6.80                                                                             42.94                                                                            5.46                                                                             11.31                                                                            6.73                                                                             [CoC.sub.31 H.sub.47 N.sub.7 ](PF.sub.                                        6).sub.2                                  169 Ex. VI  -- -- -- -- -- -- -- -- --                                        170 Ex. VIII                                                                              -- -- -- -- -- -- -- -- --                                        171 Ex XII  53.94                                                                            7.11                                                                             13.48                                                                            8.96                                                                             53.99                                                                            6.94                                                                             13.77                                                                            8.75                                                                             [FeC.sub.28 H.sub.44 N.sub.6 O.sub.2                                          ]Cl.sub.2                                 172 Ex. XVI 62.31                                                                            6.78                                                                             11.78                                                                            -- 61.65                                                                            7.10                                                                             11.59                                                                            -- [ZnC.sub.37 H.sub.48 N.sub.6 ]Cl.sub.2                                        N                                         173 Q       43.96                                                                            5.94                                                                             11.39                                                                            -- 43.78                                                                            5.85                                                                             11.53                                                                            -- [NiC.sub.34 H.sub.50 N.sub.8 ](PF.sub.                                        6).sub.2                                                                      .2CH.sub.3 OH                             174 R       56.84                                                                            7.30                                                                             15.60                                                                            -- 56.74                                                                            7.30                                                                             15.57                                                                            -- [NiC.sub.34 H.sub.50 N.sub.8 ]Cl.H.sub                                        .2 O                                      175 D       43.75                                                                            6.15                                                                             11.03                                                                            5.80                                                                             43.70                                                                            6.28                                                                             11.10                                                                            5.79                                                                             [CoC.sub.35 H.sub.54 N.sub.8 O](PF.sub                                        .6).sub.2                                                                     .2CH.sub.3 OH                             176 Q       44.41                                                                            5.48                                                                             12.19                                                                            -- 44.23                                                                            5.69                                                                             12.05                                                                            -- [NiC.sub.34 H.sub.50 N.sub.8 ](PF.sub.                                        6).sub.2                                  177 D       44.40                                                                            5.48                                                                             12.18                                                                            6.41                                                                             44.28                                                                            5.66                                                                             12.02                                                                            6.32                                                                             [CoC.sub.34 H.sub.50 N.sub.8 ](PF.sub.                                        6).sub.2                                  178 Q       46.78                                                                            5.99                                                                             11.49                                                                            6.02                                                                             46.67                                                                            6.10                                                                             11.37                                                                            6.03                                                                             [NiC.sub.38 H.sub. 58 N.sub.8                                                 ](PF.sub.6).sub.2                         179 R       53.34                                                                            8.13                                                                             13.10                                                                            -- 53.03                                                                            8.01                                                                             12.84                                                                            -- [NiC.sub.38 H.sub.58 N.sub.8 ]Cl.sub.2                                        .                                                                             .5.5H.sub.2 O                             180 D       46.77                                                                            5.99                                                                             11.48                                                                            6.04                                                                             46.60                                                                            6.28                                                                             11.22                                                                            5.88                                                                             [CoC.sub.38 H.sub.58 N.sub.8 ](PF.sub.                                        6).sub.2                                  181 F       51.27                                                                            6.91                                                                             12.59                                                                            6.27                                                                             51.17                                                                            6.97                                                                             12.18                                                                            6.55                                                                             [FeC.sub.38 H.sub.58 N.sub.8 Cl]PF.sub                                        .6                                                                            .1.5H.sub.2 O                             182 S       52.19                                                                            6.92                                                                             12.81                                                                            6.39                                                                             52.44                                                                            7.57                                                                             12.55                                                                            6.04                                                                             [FeC.sub.38 H.sub.60 N.sub.8 O](PF.sub                                        .6).sub.2                                 183 G       35.87                                                                            4.75                                                                             8.81                                                                             4.99                                                                             35.78                                                                            4.88                                                                             8.73                                                                             4.98                                                                             [CuC.sub.38 H.sub.58 N.sub.8 ](PF.sub.                                        6).sub.2                                  184 Q       52.42                                                                            5.91                                                                             9.88                                                                             5.18                                                                             52.67                                                                            6.21                                                                             10.12                                                                            5.26                                                                             [NiC.sub.48 H.sub.62 N.sub.8 ](PF.sub.                                        6).sub.2                                                                      0.7C.sub.2 H.sub.5 OH                     185 Q       49.51                                                                            5.53                                                                             10.93                                                                            -- 49.48                                                                            5.34                                                                             10.99                                                                            -- [NiC.sub.42 H.sub.59 N.sub.8 ](PF.sub.                                         6).sub.2                                 186 R       56.64                                                                            7.24                                                                             12.58                                                                            -- 56.85                                                                            7.16                                                                             12.17                                                                            -- [NiC.sub.42 H.sub.54 N.sub.8 ]Cl.sub.2                                        n                                                                             .5H.sub.2 O                               187 D       49.10                                                                            5.56                                                                             10.65                                                                            5.60                                                                             48.97                                                                            5.38                                                                             10.45                                                                            5.96                                                                             [CoC.sub.43 H.sub.58 N.sub.8 O](PF.sub                                        .6).sub.2                                 188 F       52.48                                                                            6.29                                                                             11.66                                                                            5.81                                                                             52.28                                                                            6.12                                                                             11.48                                                                            5.73                                                                             [FeC.sub.42 H.sub.54 N.sub.8 Cl]PF.sub                                        .6                                                                            .3H.sub.2 O                               189 Q       54.62                                                                            5.31                                                                             10.02                                                                            4.91                                                                             54.25                                                                            5.67                                                                             9.98                                                                             4.94                                                                             [NiC.sub.56 H.sub.58 N.sub.8 ](PF.sub.                                        6).sub.2                                                                      .0.5CH.sub.3 CN.0.5C.sub.2 H.sub.5                                            OH                                        190 Q       41.83                                                                            5.53                                                                             13.31                                                                            -- 41.92                                                                            5.67                                                                             13.16                                                                            -- [NiC.sub.33 H.sub.52 N.sub.9 ](PF.sub.                                        6).sub.2                                                                      .1.5H.sub.2 O                             191 D       38.33                                                                            4.91                                                                             12.19                                                                            5.70                                                                             38.67                                                                            5.11                                                                             11.81                                                                            5.59                                                                             [CoC.sub.33 H.sub.52 N.sub.9 ](PF.sub.                                        6).sub.2                                                                      .1.4HBr                                   192 Q       43.58                                                                            5.32                                                                             10.39                                                                            -- 43.48                                                                            5.51                                                                             10.34                                                                            -- [NiC.sub.44 H.sub.64 N.sub.9 ](PF.sub.                                        6).sub.3                                  193 Q       45.88                                                                            4.81                                                                             10.03                                                                            -- 45.76                                                                            5.01                                                                             10.03                                                                            -- [NiC.sub.48 H.sub.60 N.sub.9 ](PF.sub.                                        6).sub.3                                  194 T       49.97                                                                            5.03                                                                             8.74                                                                             -- 50.21                                                                            5.36                                                                             8.65                                                                             -- [NiC.sub.40 H.sub.48 N.sub.6 ](PF.sub.                                        6).sub.2                                  195 T + Ex. VIII                                                                          -- -- -- -- -- -- -- -- [C.sub.40 H.sub.48 N.sub.6 ](PF.sub.6)                                        .sub.2                                    196 T + Ex. VIII                                                                          -- -- -- -- -- -- -- -- [FeC.sub.40 H.sub.48 N.sub.6 ](PF.sub.                                        6).sub.2                                      + E                                                                       197 U       59.20                                                                            8.61                                                                             8.24                                                                             4.06                                                                             59.27                                                                            8.47                                                                             8.19                                                                             4.04                                                                             [NiC.sub.70 H.sub.122 N.sub.8                                                 ](PF.sub.6).sub.2                                                             1/2 CH.sub.3 CN                           198 V       -- -- -- -- -- -- -- -- [NiC.sub.44 H.sub.68 N.sub.8 ](PF.sub.                                        6).sub.2                                  199 C       -- -- -- -- -- -- -- -- [NiC.sub.30 H.sub.52 N.sub.6 ](PF.sub.                                        6).sub.2                                  200 D       42.61                                                                            6.19                                                                             9.94                                                                             6.94                                                                             42.71                                                                            6.28                                                                             9.88                                                                             6.99                                                                             [CoC.sub.30 H.sub.52 N.sub.6 ](PF.sub.                                        6).sub.2                                  __________________________________________________________________________

OXYGEN-COMPLEXING TESTS

A large number of the compounds listed in Table 2 above were subjectedto standard thermodynamic tests (which will be familiar to those skilledin the art) to determine their oxygen affinity at various temperatures,together with the changes in enthalpy and entropy associated with thereaction for the complexing of the cationic metal complex with molecularoxygen. It should be noted that, in most cases, these tests were carriedout in the presence of ligands capable of acting as the ligand Z inFormula XVIIA; thus, although the compound may be named in Table 2, andits substituents listed in Table 3, 4, 5 or 6, as a compound of FormulaXVII, for the reasons described above in solution the compound willexist as a compound of Formula XVIIA with the ligand present in thesolution entering the position Z so that the oxygen affinity beingmeasured in in fact of the related salt of Formula XVIIA having theligand available in solution as the ligand Z.

The results of the oxygen affinity tests are shown in Table 8 below, inwhich 1-Mim. indicates N-methylimidazole, An indicates acetonitrile, pyindicates pyridine, Ace indicated acetone and 311APW indicates 3:1:1acetone:pyridine:water.

                                      TABLE 8                                     __________________________________________________________________________    Cmpd.                                                                         No. Solvent    K.sub.O.sbsb.2, torr.sup.-1                                                            Degrees C.                                                                          ΔH Kcal/M                                                                      ΔS eu.                             __________________________________________________________________________    2(c)                                                                              1.5 M 1-Mim/An                                                                           <10.sup.-4                                                                             -40   --     --                                       7   1.5 M 1-Mim/An                                                                           0.0020 ± 0.0002                                                                     -40.1 --     --                                       10  1.5 M 1-Mim/An                                                                           0.0018 ± 0.0001                                                                     -19.3 --     --                                                      0.0011 ± 0.0002                                                                     -10.2 --     --                                       12  1.5 M 1-Mim/An                                                                           0.005    -40   --     --                                       17  1.5 M 1-Mim/An                                                                           0.210 ± 0.003                                                                       -30   -15.2 ± 0.6                                                                       -65 ± 2                                              0.0499 ± 0.0005                                                                     -20                                                                  0.0252 ± 0.0003                                                                     -12                                                                  0.0191 ± 0.0004                                                                     -10.1                                                                0.0066 ± 0.0002                                                                     -0.6                                                  21  1.5 M 1-Mim/An                                                                           0.66 ± 0.02                                                                         -20   -16.2 ± 0.6                                                                       -65 ± 2                                              0.215 ± 0.005                                                                       -10.1                                                                0.058 ± 0.003                                                                       +1.0                                                                 0.0186 ± 0.005                                                                      +20.0                                                                0.0094 ± 0.0005                                                                     +20.0                                                 21  2.5 M 1-Mim/H.sub.2 O                                                                    0.167 ± 0.003                                                                       +4.8  -16.7 ± 1.0                                                                       -63 ± 3                                              0.112 ± 0.002                                                                       +10                                                                  0.055 ± 0.002                                                                       +15.3                                                                0.0265 ± 0.0008                                                                     +25                                                                  0.0131 ± 0.0002                                                                     +29.8                                                                0.009 ± 0.001                                                                       +37                                                   25  1.5 M 1-Mim/An                                                                           0.017 ± 0.001                                                                       -10.2 -14.3 ± 0.6                                                                       -62 ± 2                                              0.0079 ± 0.0003                                                                     -1.5                                                                 0.0026 ± 0.0002                                                                     +8.6                                                                 0.0012 ± 0.0002                                                                     +18.6                                                 27  1.5 M 1-Mim/An                                                                           0.09     -10   -16.3 ± 0.6                                                                       -67 ± 3                                              0.025    0                                                                    0.0097   +10                                                                  0.0031   +20                                                                  0.0015   +30                                                   28  Acetone    0.03     -19   --     --                                       28  311APW     >100     -31                                                   28  Pyridine   ˜0.01                                                                            (0)   --     --                                       32  1.5 M 1-Mim/An                                                                           1.66 ± 0.05                                                                         -20.0 -16.6 ± 0.3                                                                       -64 ± 1                                              0.97 ± 0.03                                                                         -15.0                                                                0.492 ± 0.008                                                                       -10.1                                                                0.138 ± 0.002                                                                       +1.0                                                                 0.122 ± 0.004                                                                       +2.1                                                  32  2.5 M 1-Mim/H.sub.2 O                                                                    1.6 ± 0.1                                                                           +19.7 --     --                                       38  1.5 M 1-Mim/An                                                                           4.6 ± 0.1                                                                           -10.1 -17.2 ± 0.4                                                                       -62 ± 1                                              1.32 ± 0.04                                                                         +1.0                                                                 0.98 ± 0.02                                                                         +2.1                                                                 0.295 ± 0.008                                                                       +15.3                                                                0.155 ± 0.004                                                                       +20.1                                                 38  2.5 M 1-Mim/DMF                                                                          2.76 ± 0.06                                                                         +1.0  --     --                                                      1.06 ± 0.02                                                                         +10.0                                                 38  2.5 M 1-Mim/H.sub.2 O                                                                    4.5 ± 0.4                                                                           +10                                                                  1.6 ± 0.1                                                                           +19.7                                                 38  Acetonitrile                                                                             0.026    -20   --     --                                                      0.006    -10                                                   38  Ace/1M py  0.68     -20   --     --                                                      0.19     -10                                                   46  Acetone    >200     -40   --     --                                       55  1.5 M 1-Mim/An                                                                           1.27 ± 0.04                                                                         -10   -17.2 ± 0.6                                                                       -65 ± 2                                              0.64 ±  0.01                                                                        -5                                                                   0.41 ± 0.01                                                                         +1                                                                   0.24 ± 0.02                                                                         +5                                                                   0.116 ± 0.004                                                                       +10                                                                  0.071 ± 0.002                                                                       +15                                                                  0.025 ± 0.002                                                                       +20                                                   57  1.5 M 1-Mim/An                                                                           0.85 ± 0.02                                                                         0     -17.5 ± 0.4                                                                       -64 ± 2                                              0.51 ± 0.02                                                                         +5                                                                   0.31 ± 0.01                                                                         +10                                                                  0.170 ± 0.006                                                                       +15.1                                                                0.101 ± 0.005                                                                       +20                                                                  0.065 ± 0.002                                                                       +25                                                                  0.032 ± 0.001                                                                       +30                                                   61  1.5 M 1-Mim/An                                                                           ˜170 ± 7                                                                      -0.4  --     --                                       64  1.5 M 1-Mim/An                                                                           0.164 ± 0.008                                                                       -25   -14.8 ± 0.8                                                                       -63 ± 3                                              0.083 ± 0.003                                                                       -20                                                                  0.042 ± 0.002                                                                       -15.4                                                                0.026 ± 0.001                                                                       -10                                                                  0.0104 ± 0.0007                                                                     0                                                     69  1.5 M 1-Mim/An                                                                           2.46 ± 0.04                                                                         -10   -17.3 ± 0.5                                                                       -64 ± 2                                              0.80 ±  0.04                                                                        0                                                                    0.41 ± 0.01                                                                         +5                                                                   0.23 ± 0.01                                                                         +10                                                                  0.15 ± 0.01                                                                         +15                                                   71  1.5 M 1-Mim/An                                                                           4.5 ± 0.1                                                                           0     -18.6 ± 0.9                                                                       -65 ± 3                                              1.4 ± 0.1                                                                           +10                                                                  0.93 ± 0.04                                                                         +14.9                                                                0.62 ± 0.04                                                                         +19.4                                                                0.26 ± 0.01                                                                         +25                                                                  0.160 ± 0.004                                                                       +30                                                   76  1.5 M 1-Mim/An                                                                           2.3      +5    -18.0 ± 0.9                                                                       -65 ± 3                                              0.94     +10                                                                  0.51     +15                                                                  0.27     +20                                                                  0.16     +25                                                   78  1.5 M 1-Mim/An                                                                           >200     0     --     --                                       81  1.5 M 1-Mim/An                                                                           1.7 ± 0.1                                                                           0     --     --                                       83  1.5 M 1-Mim/An                                                                           5.92 ± 0.04                                                                         0     -17.2 ± 0.3                                                                       -60 ± 1                                              3.34 ± 0.04                                                                         +4.9                                                                 1.95 ± 0.04                                                                         +10                                                                  1.13 ± 0.02                                                                         +15                                                                  0.65 ± 0.02                                                                         +20                                                                  0.45 ± 0.02                                                                         +25                                                                  0.25 ± 0.01                                                                         +29.8                                                 87  1.5 M 1-Mim/An                                                                           0.0085 ± 0.0007                                                                     -40   --     --                                       94  311 Ace/Mim/H.sub.2 O                                                                    0.0019 ± 0.0001                                                                     -39   --     --                                       95  311 APW    0.16 ± 0.01                                                                         -41.5 --     --                                                      0.019 ± 0.001                                                                       -20.2                                                                0.003 ± 0.0005                                                                      0                                                     95  4/1 Ace/py 0.08 ± 0.01                                                                         -41.5 --     --                                       97  4/1 Ace/Mim                                                                              1.7 ± 0.2                                                                           -41.5 --     --                                       97  4/1 Ace/py 0.015 ± 0.003                                                                       -41.5 --     --                                       107 311 APW    0.016 ± 0.002                                                                       -34.7 -16.1 ± 1                                                                         76 ± 3                                               0.0133 ± 0.002                                                                      -34                                                                  0.0074 ± 0.0009                                                                     -26.5                                                                0.0043 ± 0.0009                                                                     -19.5                                                                0.001 ± 0.0006                                                                      0                                                     111 311 APW    0.12 ± 0.004                                                                        -20                                                   113 1.5 M 1-Mim/An                                                                           0.01     -30   --     --                                                      0.0023   -18.5                                                                0.0020   -16.4                                                 115 1.5 M 1-Mim/An                                                                           0.0012   -30   --     --                                       116 311 APW    0.125 ± 0.004                                                                       -40.5 -14.2 ± 0.5                                                                       -65 ± 2                                              0.119 ± 0.004                                                                       -39.2                                                                0.032 ± 0.002                                                                       -30                                                                  0.025 ± 0.002                                                                       -29.1                                                                0.0112 ± 0.0008                                                                     -20                                                                  0.0045 ± 0.0003                                                                     -12                                                   118 311 APW    0.55 ± 0.07                                                                         -37.7 -17.5 ± 0.4                                                                       -76 ± 2                                              0.20 ± 0.01                                                                         -32.3                                                                0.050 ± 0.001                                                                       -21.3                                                                0.0091 ± 0.002                                                                      -10.1                                                                0.0095 ± 0.003                                                                      -10.2                                                                0.0025 ± 0.0004                                                                     0                                                     118 1.5 M 1-Mim/Tol                                                                          0.022 ± 0.001                                                                       0     --     --                                       118 1.5 M 1-Mim/An                                                                           0.0155 ± 0.0009                                                                     0     --     --                                       118 1.5 M 1-Mim/H.sub.2 O                                                                    0.031 ± 0.002                                                                       0     --     --                                       118 1.5 M 1-Mim/MeOH                                                                         0.0041 ± 0.0003                                                                     0     --     --                                       118 1.5 M 1-Mim/Ace                                                                          0.0086 ± 0.0007                                                                     0     --     --                                       118 1-Mim      0.021 ± 0.001                                                                       0     --     --                                                      0.0012 ±  0.0003                                                                    +20                                                   119 311 APW    0.0325 ± 0.0009                                                                     -41.1 -15.9 ± 0.6                                                                       -75 ± 3                                              0.013 ± 0.0005                                                                      -34.2                                                                0.0065 ± 0.0003                                                                     -29.5                                                                0.0046 ± 0.0004                                                                     -29                                                                  0.00295 ± 0.0001                                                                    -23.8                                                                0.00135 ± 0.00006                                                                   -15.7                                                                0.00089 ± 0.00007                                                                   -9.8                                                  120 311 APW    0.076 ± 0.004                                                                       -34.5 -17.6 ± 0.6                                                                       -76 ± 3                                              0.034 ± 0.002                                                                       -29.8                                                                0.0073 ± 0.0005                                                                     -19.1                                                                0.0022 ± 0.0001                                                                     -9.4                                                  121 311 APW    0.026 ± 0.002                                                                       -29.8 -16.8 ± 0.4                                                                       -76 ± 2                                              0.0101 ± 0.0003                                                                     -23                                                                  0.0037 ± 0.0001                                                                     -15.4                                                                0.0025 ± 0.0001                                                                     -6.6                                                  145 1.5 M 1-Mim/An                                                                           0.114 ± 0.004                                                                       -20   -14 ± 1                                                                           -60 ± 4                                              0.053 ± 0.001                                                                       -15                                                                  0.0027 ± 0.001                                                                      -10                                                                  0.016 ± 0.001                                                                       -5                                                                   0.0099 ± 0.0006                                                                     0                                                                    0.0064 ± 0.0009                                                                     +10                                                   145 An         0.054 ± 0.007                                                                       -20   --     --                                                      0.0051 ± 0.0006                                                                     -15                                                   145 An/1 equiv p-toluic                                                                      0.011 ± 0.001                                                                       -20   --     --                                           acid                                                                                     0.0017 ± 0.0002                                                                     -15                                                   152 1.5 M 1-Mim/An                                                                           0.015 ± 0.001                                                                       -20.2 -13.8 ± 0.6                                                                       -63 ± 2                                              0.0081 ± 0.0005                                                                     -14.4                                                                0.0047 ± 0.0003                                                                     -10                                                                  0.0020 ± 0.0001                                                                     0                                                     155 1.5 M 1-Mim/An                                                                           0.014 ± 0.001                                                                       -14.8 --     --                                       158 1.5 M 1-Mim/An                                                                           >10.sup.-4                                                                             -20   --     --                                       159 Acetone    0.0055 ± 0.0001                                                                     -38.8 --     --                                       162 1.5 M 1-Mim/An                                                                           0.020 ± 0.001                                                                       -37.6 --     --                                                      0.0099 ± 0.0003                                                                     -33.2                                                                0.0037 ± 0.0002                                                                     -25.0                                                 163 Acetone    0.223 ± 0.006                                                                       -41   -14.2 ± 0.2                                                                       -64 ± 2                                              0.212 ± 0.008                                                                       -40.6                                                                0.1181 ± 0.009                                                                      -34.9                                                                0.048 ± 0.004                                                                       -29.7                                                                0.044 ± 0.004                                                                       -29.3                                                                0.0315 ± 0.002                                                                      -25.0                                                                0.019 ± 0.002                                                                       -20.5                                                 168 Acetonitrile                                                                             0.004    -20   --     --                                                      0.001    -10                                                   168 Acetone    0.004    -20   --     --                                                      0.001    -10                                                   168 H.sub.2 O  0.003    +2    --     --                                       180 Acetonitrile                                                                             0.075 ± 0.013                                                                       -16.3 --     --                                                      0.053 ± 0.003                                                                       -7.9                                                                 0.020 ± 0.002                                                                       -6.2                                                                 0.021 ± 0.002                                                                       +0.9                                                                 0.024 ± 0.001                                                                       +6.6                                                                 0.036 ± 0.002                                                                       +8.5                                                                 0.051 ± 0.008                                                                       +10.5                                                 180 1.5 M 1-Mim/An                                                                           31 ± 7                                                                              +1    --     --                                       __________________________________________________________________________

As mentioned above, for practical use in separating oxygen from theatmosphere, it is desirable that the value of the equilibrium constantbe in the range of 0.003 to 0.1 torr⁻¹, with the range of 0.01-0.03being especially valuable. Accordingly, based upon the results in Table8 above, the following salts, solvents and temperature ranges arerecommended for use in separating oxygen from air. It will be seen thatcompounds 21, 27, 55, 57, 118 and 145 are likely to be especially usefulsince their equilibrium constants are within the desired range at aboutambient temperature.

                  TABLE 9                                                         ______________________________________                                        Cmpd.               Temp. Range,                                              No.   Solvent       °C. K.sub.O.sub.2, range, torr.sup.-1              ______________________________________                                        7     1.5 M 1-Mim/An                                                                              -40        0.002                                          10    1.5 M 1-Mim/An                                                                              -30        0.003                                          12    1.5 M 1-Mim/An                                                                              -40        0.005                                          17    1.5 M 1-Mim/An                                                                              -25 to 0   0.1 to 0.005                                   21    1.5 M 1-Mim/An                                                                              -5 to +25  0.1 to 0.005                                   21    2.5 M 1-Mim/H.sub.2 O                                                                       +10 to +40 0.1 to 0.005                                   25    1.5 M 1-Mim/An                                                                              -10 to +8  0.02 to 0.003                                  27    1.5 M 1-Mim/An                                                                              -10 to +20 0.1 to 0.003                                   28    acetone       -20        0.03                                           28    pyridene      0          0.01                                           32    1.5 M 1-Mim/An                                                                              -20 to +2  1.66 to 0.12                                   38    acetonitrile  -20 to -10 0.03 to 0.005                                  38    acetone/1M py -5         0.1                                            55    1.5 M 1-Mim/An                                                                              +10 to +30 0.1 to 0.005                                   57    1.5 M 1-Mim/An                                                                              +20 to +40 0.1 to 0.008                                   64    1.5 M 1-Mim/An                                                                              -22 to +10 0.1 to 0.003                                   69    1.5 M 1-Mim/An                                                                              +20        0.1                                            87    1.5 M 1-Mim/An                                                                              -40        0.009                                          95    3/1/1 ace/py/H.sub.2 O                                                                      -40 to 0   0.15 to 0.003                                  95    4/1 acetone/py                                                                              -40        0.08                                           97    4/1 acetone/py                                                                              -40        0.02                                           107   3/1/1 ace/py/H.sub.2 O                                                                      -35 to -20 0.17 to 0.004                                  111   3/1/1 ace/py/H.sub.2 O                                                                      -20        0.12                                           113   1.5 M 1-Mim/An                                                                              -30 to -20 0.01 to 0.003                                  116   3/1/1 ace/py/H.sub.2 O                                                                      -39 to -12 0.1 to 0.004                                   118   3/1/1 ace/py/H.sub.2 O                                                                      -25 to 0   0.1 to 0.003                                   118   1.5 M 1-Mim/toluene                                                                         0          0.02                                           118   1.5 M 1-Mim/An                                                                              0          0.02                                           118   1.5 M 1-Mim/H.sub.2 O                                                                       0          0.03                                           118   1.5 M 1-Mim/MeOH                                                                            0          0.004                                          118   1.5 M 1-Mim/acetone                                                                         0          0.009                                          118   Mim           0 to +20   0.02 to 0.001                                  119   3/1/1 ace/py/H.sub.2 O                                                                      -40 to -24 0.03 to 0.003                                  120   3/1/1 ace/pyH.sub.2 O                                                                       -35 to -10 0.08 to 0.002                                  121   3/1/1 ace/pyH.sub.2 O                                                                       -30 to -15 0.03 to 0.003                                  145   1.5 M 1-Mim/An                                                                              -20 to +15 0.1 to 0.003                                   145   acetonitrile  -20        0.05                                           152   1.5 M 1-Mim/An                                                                              -20 to -8  0.02 to 0.003                                  155   1.5 M 1-Mim/An                                                                              -15        0.01                                           159   acetone       -40        0.006                                          162   1.5 M 1-Mim/An                                                                              -40 to -25 0.02 to 0.003                                  163   acetone       -35 to -10 0.1 to 0.003                                   168   acetonitrile  -20        0.004                                          168   acetone       -20        0.004                                          168   H.sub.2 O     2          0.003                                          ______________________________________                                    

It should be noted that, in some cases, synthesis of a nitrogen-nitrogenbridged salt of Formula I produces as a by-product a corresponding salthaving a dimeric cation of the Formula XIX shown in FIG. 5 of theaccompanying drawings. As indicated in method B above, the resultantmixture of monomeric compound of Formula I and dimeric compound ofFormula XIX can be separated by chromatography upon a ion exchangeresin; the monomeric compound is eluted by a 0.2M aqueous solution ofsodium sulphate, while the dimeric compound is not, being eluted onlywith a 0.4M aqueous sodium sulphate solution. The monomeric and dimericcomplexes can readily be distinguished; as already indicated, the twocompounds differ in the concentration of aqueous sodium sulfate solutionnecessary to elute them from an ion exchange resin. A second method ofdistinguishing the two compounds is to deprotonate the cations with apowerful base such as an alkoxide, whereupon the cationic monomer anddimer are converted into neutral molecules suitable for molecular weightdeterminations. The dimer and monomer can then be distinguished bymolecular weight determinations using, for example, vapor pressureosmometry or (in many cases where the neutral species are sufficientlyvolatile) by mass spectrometry. Thirdly, in many cases the monomeric anddimeric cations can be distinguished by proton nuclear resonancespectrometry. Further details as to distinguishing between the monomericand dimeric salts are given in the paper entitled "Synthesis andCharacterization of a Novel Family of Dimeric Nickel (II)Complexes-Bi-metallic Species Separated by a Persistent Void" by Buschet al in J.A.C.S., 103, 5107 (1981).

EXAMPLES 201-212

These examples illustrate the preparation of compounds of Formula I inwhich the bridging groups X and Y are not identical. Also, theseexamples illustrates the formation of a compound of Formula I in whichthe bridging group R is a dodecamethylene group.

The synthetic route employed is shown in FIG. 8 of the accompanyingdrawings. The starting material of Formula XXVII was prepared by theprocedure described in Riley, D. P., PhD. thesis, The Ohio StateUniversity, Columbus, Ohio (1975) and in Riley et al, InorganicSynthesis, 18, 36(1978). The compound of Formula XXVII was a brightorange powder and was obtained in a yield of 79%. Formation of atrimethylene group Y to produce the compound of Formula XXVIII waseffected by refluxing 50 g. of the compound of Formula XXVII inapproximately 300 ml. of 1,3-diaminopropane (freshly distilled frompotassium hydroxide) for 15 minutes. The very dark, hot solution wasthen poured into 1.51. of vigorously stirred water to precipitate alight pink product in a yield of 84%. The product was thoroughly driedand chromatographed on alumina, eluting with chloroform. This solventwas removed, the resulting solid ground to a dark pink powder and thispowder dried in a vacuum of about 60° C.

The resultant compound of Formula XXVIII was methylated to produce thecompound of Formula XXIX by dissolving 10 g. of the compound of FormulaXXIX in approximately 30 ml. of methylene chloride, freshly distilledfrom phosphorous pentoxide. 5 ml. of CH₃ OSO₂ F was added and thesolution stirred overnight at room temperature. The resultant solutioncontains some suspended material, but this was redissolved by additionof 20 ml. of methanol to yield a light yellow/brown solution which wasthen reduced to dryness on a rotary evaporator to yield a brown oil. Afiltered solution of 10 g. of ammonium hexafluorophosphate in 20 ml. ofmethanol was added to this oil and the solution vigorously swirled untila precipitate appeared (in some cases difficulty is experienced ininitiating precipitation, but precipitation could always be begun byadding approximately 1-2 ml. of acetonitrile). Crystallization wasallowed to continue for several hours at room temperature and thesolution was filtered to yield a bright green/yellow solid in a yield of50 to 80%. This material darkened on standing for several weeks in airand if stored for substantial periods before being used in the followingstep of the process needed to be recrystallized fromacetonitrile/methanol.

As shown in FIG. 8, introduction of the nitrogen-nitrogen bridge intothe compound of Formula XXIX to produce a compound of Formula XXX (whichis, of course, also a compound of Formula I having M=Ni, n=2, R₁=hydrogen, R₂ =methyl, X=ethylene and Y=trimethylene) was effected byreaction with the appropriate alpha, omega-diamine. 10 g. (0.027 mole)of the compound of Formula XXIX and 0.027 mole of the diamine wereseparately dissolved in 300 ml. aliquots of acetonitrile and wereinjected into 200 ml. of stirred, refluxing acetonitrile over a periodof 5 to 6 hours using a peristaltic pump. A very dark solutioninvariably resulted and carrying out the reaction under nitrogen did notimprove the color. The volume of the solution was then reduced to about20 ml. on a rotary evaporator and the resultant liquid chromatrographedon alumina eluting with acetonitrile. This chromatographic separationproduced a yellow or red, fast-moving band followed by, but notcompletely resolved from a dark material. The red or yellow band wasseparated as far as possible from the dark material, reconcentrated andrechromatographed on fresh alumina, this time eluting with methylenechloride or methylene/chloride acetone. The red or yellow material wascollected, evaporated to dryness on a rotary evaporator and dissolved inapproximately 100 ml. of acetone. Water was added to the acetonesolution until a precipitate formed which was then just redissolved bythe addition of further acetone to give approximately 300 ml. ofsolution, which was passed through a 30 ml. frit half filled with CMSephadex resin under suction. The light yellow filtrate was furtherdiluted with approximately 200 ml. of water and again passed throughfresh CM Sephadex resin to yield a substantially clear filtrate.

The Sephadex resin containing the compound was loaded onto a 4×20 cm.column of the same resin by pouring it into a column of water above theresin column so that a distinct layer of compound-containing resin wasobtained. The column was then topped of with a layer of sand. Elutionwith 0.2M sodium sulfate produced a red band followed by, but separatedfrom, dark material. The red band was collected and the product ofFormula XXX precipitated by addition of ammonium hexofluorophosphate; ifa ¹³ C NMR spectrum showed that the compound was still impure, it wasrechromatographed on Sephadex resin.

The compounds prepared in this manner and the yields obtained were asfollows:

    ______________________________________                                        Compound No.  R         R.sub.4    Yield                                      ______________________________________                                        201           (CH.sub.2).sub.5                                                                        CH.sub.3   8%                                         202           (CH.sub.2).sub.6                                                                        CH.sub.3   33%                                        203           (CH.sub.2).sub.7                                                                        CH.sub.3   20%                                        204           (CH.sub.2).sub.8                                                                        CH.sub.3   7%                                         205           (CH.sub.2).sub.12                                                                       CH.sub.3   4%                                         206            m-xylylene                                                                             H          10%                                        207           (CH.sub.2).sub.5                                                                        H          6%                                         208           m-xylylene                                                                              CH.sub.3   15%                                        ______________________________________                                    

Compounds 201-204 were converted to the corresponding cobalt complexesby demetallating by the method of Example VIII above, then insertingcobalt by a variant of Method D above, again carried out under anitrogen atmosphere, in which 0.1 g. of the ligand salt is stirredovernight with 0.05 g. of cobalt acetate tetrahydrate and 0.1 g. ofsodium acetate trihydrate at room temperature in 20 ml. of methanol.Analytical data for the cobalt complexes thus prepared were as follows:(in all three cases, R₄ is a methyl group and the anion ishexfluorophosphate; compound 209 only crystallizes with 1 molecule ofwater of crystallization):

Compound 209, R═(CH₂)₆ : Calculated: C, 37.84%; H, 5.59%; N, 10.59%.Found: C 37.12%; H, 5.56%; N, 10.30%.

Compound 210, R=(CH₂)₇): Calculated: C 39.55%, H, 5.61%; N, 10.64%.Found: C 39.48%; H, 5.62%; N, 10.62%.

Compound 211, R=(CH₂)₈. Calculated: C, 40.35%, H, 5.77%, N, 10.45%.Found: C 41.32%; H, 6.03%; N, 10.72%.

Compound 208 was also converted to the corresponding Fe(II) complex bydemetallating by the method of Example VIII above, followed by insertionof Fe²⁺ by Method E above. The resultant iron complex, compound 212,gave the following elemental analysis:

C₂₇ ; H₃₈ ; N₆ ; Fe; Cl; PF₆.H₂ O: Calculated: C, 46.28%; H, 11.99%; N,5.71%; Fe, 7.97%. Found: C, 46.41% H, 12.12%; N, 5.59%; Fe, 7.95%.

Oxygen Affinity Tests

Solutions of the cobalt complexes, compounds 209-211 above were made in1.5 Molar N-methylimidazole in acetonitrile so that an absorption of1.5-2.6 was obtained at about 380 mn. The spectral differences weremeasured at 420, 440 and 460 nm. at 20° C. Good isosbestic points wereobtained at 390 and 530 mn. The nickel complex, 205, having R=(CH₂)₁₂was also converted to the corresponding cobalt complex in very low yieldin the same manner as the other complexes and thisdodecamethylene-bridged cobalt complex exhibited a very high oxygenaffinity; some decomposition occured when pure oxygen was bubbled for along time through the solution, but the spectrum remained isosbestic foroxygen pressures up to 38 torr at 20° C.

The measured oxygen affinities for compound 209-211 were as follows:

    ______________________________________                                        Compound No.    K.sub.02, Torr.sup.-1                                         ______________________________________                                        209             0.52                                                          210             1.32                                                          211             5.2                                                           ______________________________________                                    

These oxygen affinities are all measured at 20° C., and in all cases aremuch lower than the oxygen affinities of the corresponding compounds inwhich both X and Y are trimethylene bridges. It is believed (althoughthe invention is in no way limited by this belief) that the substitutionof an ethylene group for a trimethylene group as the group X tends toproduce a flatter macrocycle, thus producing a smaller cave for oxygento enter and reducing oxygen affinity.

EXAMPLE 213

This example illustrates the attachment of various compounds of FormulaXVII to polymeric supports.

(A) Compound No. 32

Compound No. 32 was deprotonated with sodium methoxide, thereby removingthe two protons R₄. The deprotonated compound was then run through a 6%crosslinked polystyrene polymer containing 3 meq/g of benzyl chloridegroups, thereby attaching compound No. 32 to the polymer via covalentbonds between the two nitrogens in the bridge and separate benzylgroups.

Upon exposure to molecular oxygen at a pressure of 1 atmosphere, thepolymer-supported compound slowly absorbed molecular oxygen, as shown bythe electron paramagnetic resonance spectrum. The resultant molecularoxygen complex was stable for weeks, de-oxygenated slowly on standing inthe absence of oxygen and could be re-oxygenated, although minorirreversibility was demonstrated in the EPR spectrum, apparently due toirreversible decomposition of the oxygen complex.

Compound No. 32 was also attached to a similar polymer having only 1%crosslinking; the loading of compound No. 32 was 0.06 meq/g. of polymer.Again, upon exposure to oxygen at a pressure of 1 atmosphere the EPRspectrum showed the formation of an oxygen complex stable for at leastone week at room temperature.

(B) Compound No. 38

Compound No. 38 was added to Porapak S, a commercially-availablepolyvinylpyridine polymer. The compound became attached to the polymerby coordination of the cobalt ion to the pyridine groups on the polymer,the pyridine functioning as the axial ligand, in effect transformingcompound 38 into the corresponding compound of Formula XVII A having apyridine ligand Z. Upon exposure to molecular oxygen, thepolymer-supported compound formed a molecular oxygen adduct, asdemonstrated in the change in the EPR spectrum, and this adduct wasstable as a dry solid for several days at room temperature. Vacuumpumping removed only part of the molecular oxygen from the oxygen adductand after prolonged standing at room temperature organic radical specieswere visible as shown by the EPR spectrum of the adduct.

Compound No. 38 was also attached to control pore glass aminopropylpolymer in the same manner; in this case, attachment of the polymer tothe compound took place via coordination of an aminopropyl group on thepolymer to the cobalt ion of compound No. 38. Upon exposure to molecularoxygen, an oxygen adduct was formed, as indicated by the EPR spectrum.This adduct was stable for several days at room temperature in a sealedtube.

(C) Compound No. 25

Compound No. 25 was attached to Porapak S in the same way as describedin part (B) of this Example above. The properties of thepolymer-supported compound were generally similar to those of compoundNo. 38 on the same polymer except that, on standing in a sealed tube,the molecular oxygen adduct regenerated the unoxygenated form ofCompound No. 25 in addition to a radical species. The regenerated cobaltcomplex would be reoxygenated and the cycle repeated.

EXAMPLE 214

This example illustrates the attachment of a compound of Formula XIX Ato a polymer.

The compound of Formula XIX A having M^(n+) =Co²⁺, X=Y=(CH₂)₃, R₁=hydrogen, R₂ =R'₃ =R₄ =R'₆ =CH₃ was attached to Porapak S in the samemanner as described in Example 213 (B) above. Again, on exposure tomolecular oxygen, the polymer-supported compound produced an oxygenadduct which, upon standing in a sealed tube at room temperature for anextended period regenerated the unoxygenated form of thepolymer-supported compound; this unoxygenated form could bereoxygenated. The EPR spectrum gave no evidence for the formation of theradical species generated upon standing, so that the oxygen adductformation reaction appears to be substantially completely reversible.

EXAMPLE 215

This example illustrates the preparation of a compound of Formula XX andthe formation of an oxygen adduct thereof.

(A) 1,1,12,12-Tetraacteyldodecane

60 g (0.6 mole) of 2,4-pentanedione were added to a solution of 15.6 g.(0.4 mole) of potassium metal in 450 ml. of t-butyl alcohol contained ina one liter three-necked flask fitted with a water condensor. Theresulting milky white solution was refluxed for 30 minutes and then 60g. (0.2 mole) of 1,10-dibromodecane were added over a five minute periodvia a pressure-equalizing dropping funnel. The resultant mixture wasrefluxed for another hour and then 8 g. of potassium iodide were added,after which the mixture was refluxed for a further 48 hours.

Three-quarters of the alcohol solvent was distilled off and theremaining mixture washed with 200 ml. of water, then extracted with 200ml. of benzene. After separation of the benzene from the reactionmixture, the benzene was dried over anhydrous sodium sulfate for 24hours and then the benzene removed in a rotary evaporator until an oilwas obtained. Storage of this oil under pentane in a refrigeratorproduced gradual solidification of the desired tetraacetylododecaneafter prolonged standing. The yield was 55% based upon the pentanedioneand the product had the expected NMR and IR spectra: ¹³ C N MR: 204.3,68.9, 30.6, 29.3, 28.9, 28.8, 27.9 and 27.2 ppm. IR: 3400 (w, hydroxyl),1720 (vs,b, carbonyl) and 1580 (m,sh, enol-chelate) cm⁻¹.

(B) Condensation with ethylenediamine

2 g. (0.006 mmole) of the 1,1,12,12-tetraacetyldodecane prepared as thusdescribed was dissolved in 1 liter of dry ethanol. 0.36 g. (0.006 mole)of ethylenediamine was dissolved separately in 1 liter of dry ethanol.The two ethanolic solutions were then allowed to drip via separatepressure-equalizing dropping funnels into a 3-liter, three-necked flaskcontaining 500 ml. of boiling ethanol, the total addition of the twosolutions taking 6 hours. Condensation of the tetraacetyldodecane withthe ethylenediamine thus took place under extremely high dilutionconditions, thereby reducing as far as possible any tendency forpolymerization. After the addition of the two ethanolic solutions to theflask have been completed, the resultant solution was refluxed for afurther 24 hours and the solvent removed by rotary evaporation until thevolume of the reaction mixture had been reduced to about 50 ml. Theproduced was precipitated by addition of about 100 ml. of dry ethylether to the solution followed by filtration and purified byrecrystallization from ether. The yield of the product (the compound ofFormula XX in which R₇ is (CH₂)₁₀ and R₈ is (CH₂)₂ was 1.9 g. (88%).

To confirm that the desired product was obtained, a ¹³ C N MR spectrumwas run. This spectrum showed peaks at 195.4, 162.0, 105.0, 43.7, 31.4,29.7, 29.4, 27.5 and 14.4, ppm. This spectrum was very different fromthat of the tetraketone starting material, but closely similar to thatof the previously known "acacen" ligand (a compound similar to thecompounds of Formula XX having R₈ =(CH₂)₂, but with the bridging groupR₇ replaced by two hydrogen atoms); the acacen ligand has a ¹³ C MMRspectrum with peaks at 195.4, 162.7, 96.1, 43.5, 28.8 and 18.5 ppm.Furthermore, a molecular weight determination on the compound inchloroform solution indicated that it was indeed monomeric.

(C) Preparation of Nickel (II) Complex

0.2 g. (0.00055 mole) of the compound of Formula XX prepared in part (b)of this Example was dissolved in 60 ml. of dry, hot ethanol and added toa solution of 0.1 g. (0.0004 mole) of nickel (II) of acetatetetrahydrate in 60 ml. of hot dry, hot ethanol. The mixture turned deepbrown in color and a fine flocculant precipate formed, which was removedby filtration. The brown filtrate was reduced in volume and dry diethylether added thereto to precipitate the nickel complex as a brownamorphous solid in a yield of 54%.

The nickel complex was found to be monomeric by molecular weightdetermination in chloroform solution. Furthermore, the structure wasconfirmed by a ¹³ C N MR spectrum which was closely similar to that ofthe nickel (II) complex of acacen; the ¹³ C spectrum of the nickelcomplex of the invention showed peaks at 173.8, 165.0, 106.9, 53.9,31.2, 30.4, 29.6, 29.5, 24.2 and 17.9 ppm, closely analogous to thecorresponding spectrum of the acacen complex which shows peaks at 176.6,164.4, 99.4, 52.0, 24.2 and 17.9 ppm--the only bands in the spectrum ofthe instant complex not closely analogous to the acacen complex areattributable to the methylene bridge.

(D) Preparation of Cobalt (II) Complex

0.15 g. (0.000414 mole) of the compound of Formula XX produced in part Bof this Example was dissolved in 10 ml. of dry, boiling methanol andadded to a solution of 0.1 g. (0.000414 mole) of cobalt (II) acetatetetrahydrate and 0.11 g. (0.0005 mole) of sodium acetate trihydrate in20 ml. of boiling methanol. The purple solution of the cobalt acetateimmediately turned orange upon addition of the compound of Formula XXand a fine flocculant precipitate appeared. The mixture was then stirredfor an additional three hours at room temperature and the solventremoved under vacuum. The solid residue obtained was extracted with 10ml. of dry toluene.

The entire preparation of the cobalt complex was carried out in an inertatmosphere glove box. The yellow solid isolated produced no resolvableEPR spectrum in toluene at liquid nitrogen temperature or above, butthis was not unexpected since it has been observed for the correspondingacacen complex and appears to be a common phenomenon; see for example,Hoffman et al, J.A.C.S., 92, 61 (1970).

Addition of pyridine to a toluene solution of the cobalt complex readilyproduced the corresponding complex having a pyridine axial ligand, andthis pyridino complex yielded, in frozen toluene solution, a EPRspectrum indicating near axial symmetry about the cobalt ion but withthe perpendicular region split by a rhombic distortion. All eight ⁵⁹ Cohyperfine lines (I=7/2 for ⁵⁹ Co) were observable for the high fieldparallel component, and several of these lines were split into tripletsof equal intensity by the single nitrogen of the single coordinatedpyridine molecule.

When molecular oxygen was admitted to a sample tube containing asolution of the pyridino cobalt complex at -40° C., an EPR spectrumcharacteristic of a cobalt (II)/molecular oxygen adduct was obtained.The spectrum showed clear evidence of interaction of molecular oxygenwith only a single cobalt atom and the expected eight line hyperfinecoupling due to ⁵⁹ Co was observed in both the parallel andperpendicular components.

It will be apparent to those skilled in the art that numerous changesand modifications can be made in the compounds and processes of theinvention without departing from the scope thereof. In particular, Iconsider that it should be possible to prepare compounds havingproperties similar to those already described but having differentvalues of the substituents in Formulae XVII, XVIIA, I, IA, II, IIA, III,IIIA, XVIII, and XVIIIA having properties similar to those of thecompounds already described. In particular, I have very recentlyobtained very preliminary results which indicate that it is possible(using the methods described above for the synthesis of compounds ofFormulae XVIII and XVIIIA) to prepare similar compounds in which thelinkage between the two piperazine rings, --CH₂ --D--CH₂ -- in FormulaeXVIII and XVIIIA is replaced by a different linkage. My aforementionedpreliminary results indicate that this linkage could be a methylene orethylene linkage. For obvious reasons, it should be possible to preparesimilar compounds with other polymethylene linkages or with linkages ofthe formula --CO--polymethylene--CO--. It is probably also possible toprepare similar compounds in which this linkage is a phenylene or otheraromatic nucleus.

More generally, I would suggest that the metal M could be rhodium,ruthenium or platinum and that the oxidation state n+ could differ fromthose already given. Each group R₁, R₂, R₃, R₄ could be any of a widevariety of organic groups or heterocyclic groups, for example alkylgroups, aryl groups, fluorinated alkyl groups or (as mentioned brieflyabove) various types of polymeric groups; preferably the alkyl groupsand fluorinated alkyl groups would not contain more than about 22 carbonatoms. The aryl groups could include phenyl, benzyl, tolyl and the likealthough substituted, fused rings and various other groups might beused. R₃ and R₄ could each be virtually any aliphatic, cycloaliphatic,aliphatic-aromatic or aromatic groups, optionally containing linkagesvia nitrogen or sulphur atoms and substituted by alkyl, aryl, carboxyl,cycloalkyl or fused aromatic rings and the like. I also consider that Xand Y could be ethylene, trimethylene or o-phenylene groups substitutedby alkyl groups, aryl groups, carboxyl groups or cycloalkyl groups orthe like, or indeed X and Y could also be fused ring groups related too-phenylene.

I also consider that the bridges R and R₅ can be any of a wide varietyof organic groups, heterocyclic groups or metalloorganic chelatescomprising two organic groups coordinated to a metal atom, For example,R and R₅ could each be a cyclohexylene or cycloheptylene groups,optionally substituted with, for example, alkyl, amino or other similarsubstituents all containing nitrogen or sulfur atoms within the ring orside-chains. Also, R and R₅ could be, for example, a m- or p-phenylenegroup or a group comprising multiple fused aromatic rings derived fromsuch a m- or p-phenylene group. Further possibilities for the bridges Rand R₅ include aliphatic and aromatic groups containing hetero atoms andsubstituted derivatives thereof.

In view of the possibility of the aforementioned modifications, theentire foregoing description is to be construed in an illustrative andnot in a limitative manner, the scope of the invention being definedsolely by the appended claims.

I claim:
 1. A salt of a cationic metal complex of the formula: ##STR17##wherein: M is Co, Fe, Cu, or Mn;n+ is a positive oxidation state of M, nbeing not greater than 3; X and Y are each independently an o-phenylene,ethylene, trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl substitutedtrimethylene or 2-(N-methyl-2-pyridino)-trimethylene group; each R₁independently is hydrogen or a methyl group; each R₂ independently ishydrogen or a methyl group; each R₃ independently is hydrogen, an alkylgroup containing not more than about 17 carbon atoms, a benzyl group, aphenyl group, or a phenyl group substituted by a halogen atom or by oneor two methoxy groups; or the two R₃ groups together form acarbon-carbon bridge, said carbon-carbon bridge comprising apolymethylene bridge containing from 7 to about 12 carbon atoms or an m-or p-xylylene group; each R₄ independently is hydrogen, an alkyl groupcontaining not more than about 4 carbon atoms, a cyanoalkyl groupcontaining not more than about four carbon atoms, a phenyl group or abenzyl group; each R₆ independently is hydrogen or a methyl group; orthe two R₆ groups together form a nitrogen-nitrogen bridge, saidnitrogen-nitrogen bridge comprising a polymethylene group containingfrom 4 to about 12 carbon atoms, a polymethylene group containing from 4to about 12 carbon atoms and substituted by a methoxycarbonyl group, ora grouping of the formula:

    --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --

where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylenegroup, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group,a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylenegroup, a sulfur atom, an imino group, or a methylimino group, subject tothe proviso that when G is a sulfur atom, a imino group or a methyliminogroup, the sum of a and b is at least 4; or the two NR₄ R₆ groupstogether form a bis-piperazino bridge of the formula ##STR18## where Dis a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene groupsubstituted by one or more methyl groups, a 9,10-anthracene group or a2,6-pyridylene group, subject to the proviso that when the two R₃ groupsdo not form a carbon-carbon bridge, either the two R₆ groups must form anitrogen-nitrogen bridge or the two NR₄ R₆ groups must form abis-piperazino bridge.
 2. A salt according to claim 1 wherein the anionis selected from the group comprising hexafluorophosphate,tetrachlorozincate, perchlorate, hexafluoroarsenate, fluoroborate,trifluoromethylsulfonate and the halides.
 3. A salt according to claim 1wherein M^(n+) is Co²⁺, Co³⁺, Fe²⁺, Fe³⁺, Cu²⁺, Mn²⁺ or Mn³⁺.
 4. A saltaccording to claim 1 wherein each R₁ is hydrogen.
 5. A salt according toclaim 1 wherein each R₂ is a methyl group.
 6. A salt according to claim1 wherein each R₃ is hydrogen, a methyl group, a phenyl group, a t-butylgroup, an n-heptyl group, an n-heptadecyl group, a 4-methoxyphenylgroup, a 4-chlorophenyl group, a 4-fluorophenyl group or a3,5-dimethoxyphenyl group, or the two R₃ groups together form apolymethylene group containing 7 to 12 carbon atoms or a m-xylylenegroup.
 7. A salt according to claim 1 wherein each R₄ is hydrogen, amethyl group, an n-propyl or n-butyl group, a 2-cyanoethyl group or abenzyl group.
 8. A salt according to claim 1 wherein two R₆ groupstogether form a nitrogen-nitrogen bridge, said nitrogen bridgecomprising a polymethylene bridge of 4 to about 8 carbon atoms, an m- orp-xylylene group, a (5-methoxy)-m-xylylene group, a --(CH₂)₃--(9,9-fluorylene)--(CH₂)₃₋ group, a --(CH₂)₄ CH(COOCH₃)(CH₂)₄ -- group,a --CH₂ --(1,3-cyclohexylene)--CH₂ -- group, a --(CH₂)₂ C(CH₃)₂ (CH)₂ --group, a 3-thiapentamethylene group, a 3-thiahexamethylene group, a--CH₂ --(5-methoxycarbonyl-1,3-phenylene)--CH₂ -- group, a2,6-pyridylene group, a 4-azaheptamethylene group, or a4-aza-4-methylheptamethylene group.
 9. A salt according to claim 2wherein said anion is hexafluorophosphate or chloride.
 10. A saltaccording to claim 1 wherein X is an ethylene group, a trimethylenegroup, a 2-(2-pyridyl)-trimethylene group, or a2-(N-methyl-2-pyridino)-trimethylene group and Y is a trimethylenegroup.
 11. A salt according to claim 1 wherein said cationic metalcomplex is of the formula ##STR19## wherein: M, n⁺, R₁, R₂, R₃, R₄, Xand Y are as defined in claim 1;each R₃ independently is hydrogen, analkyl group containing not more than about 17 carbon atoms, a benzylgroup, a phenyl group, or a phenyl group substituted by a halogen atomor by one or two methoxy groups; and R is a polymethylene groupcontaining from 4 to about 12 carbon atoms, a polymethylene groupcontaining from 4 to about 12 carbon atoms and substituted by amethoxycarbonyl group, or a grouping of the formula --(CH₂)_(a)--G--(CH₂)_(b) -- where a and b are each independently 1, 2 or 3 and Gis a 1,3-phenylene group, a 1,4-phenylene group, a methoxy-substituted1,4-phenylene group, a 9,9-fluorylene group, a 1,3-cyclohexylene group,a 1,4-cyclohexylene group, a sulfur atom, an imino group or amethylimino group, subject to the proviso that when G is a sulfur atom,a imino group or a methylimino group, the sum of a and b is at least 4.12. A salt according to claim 11 wherein the anion ishexafluorophosphate, tetrachlorozincate, perchlorate,hexafluoroarsenate, fluoroborate, trifluoromethylsulfonate and thehalides.
 13. A salt according to claim 11 where M^(n+), is Co²⁺, Co³⁺,Fe²⁺, Fe³⁺, Cu²⁺, Mn²⁺ or Mn³⁺.
 14. A salt according to claim 11 whereinX is an ethylene group, a trimethylene group, a 2,2-dimethyl-trimethylene group, a 2-(2-pyridyl)-trimethylene group or a2-(N-methyl-2-pyridino)-trimethylene group and Y is a trimethylenegroup.
 15. A salt according to claim 14 wherein X and Y are each atrimethylene group.
 16. A salt according to claim 11 wherein each R₁ ishydrogen and each R₂ is a methyl group.
 17. A salt according to claim 11where each R₃ is hydrogen, a methyl group, a phenyl group, a t-butylgroup, an n-heptyl group, an n-heptadecyl group, a 4-methoxyphenylgroup, a 4-chlorophenyl group, a 4-fluorophenyl group or a3,5-dimethoxyphenyl group.
 18. A salt according to claim 11 where eachR₄ is hydrogen, a methyl group, an n-propyl or n-butyl group, a2-cyanoethyl group or a benzyl group.
 19. A salt according to claim 11wherein R is a polymethylene bridge of 4 to about 8 carbon atoms, an m-or p-xylylene group, a (5-methoxy)-m-xylylene group, a --(CH₂)₃--(9,9-fluorylene)--(CH₂)₃ -- group, a --(CH₂)₄ CH(COOCH₃)CH₂)₄ --group, a --(CH₂ --(1,3-cyclohexylene)--CH₂ -- group, a --(CH₂)₂ C(CH₃)₂(CH)₂ -- group, a 3-thiapentamethylene group, a 3-thiahexamethylenegroup, a --CH₂ --(5-methoxycarbonyl-1,3-phenylene)--CH₂ -- group, a2,6-pyridylene group, a 4-azaheptamethylene group, or a4-aza-4-methylheptamethylene group.
 20. A salt according to claim 12wherein said anion is hexafluorophosphate or chloride.
 21. A saltaccording to claim 20 wherein M^(n+) is Co²⁺, Co³⁺, Fe²⁺, Fe³⁺, Mn²⁺,Mn³⁺ or Cu²⁺, X is an ethylene group, a trimethylene group, a2,2-dimethyltrimethylene group, a 2-(2-pyridyl)-trimethylene group or a2-(N-methyl-2-pyridino)-trimethylene group, Y is a trimethylene group,each R₁ is hydrogen, each R₂ is a methyl group, each R₃ is hydrogen, amethyl group, a t-butyl group, an n-heptyl group a 4-methoxyphenylgroup, a 4-chlorophenyl group, a 4-fluorophenyl group, or a3,5-dimethoxyphenyl group, R₄ is hydrogen or a methyl group and R is apolymethylene group containing 4 to 8 carbon atoms, an m-xylylene groupor a p-xylylene group.
 22. A salt according to claim 21 where M iscobalt or iron.
 23. A salt according to claim 21 wherein M is copper ormanganese.
 24. A salt according to claim 1 wherein said cationic metalcomplex is of the formula ##STR20## wherein: M, n⁺, R₁, R₂, X and Y areas defined in claim 1;each R₄ independently is hydrogen, an alkyl groupcontaining not more than about 4 carbon atoms or a benzyl group; each R₆independently is hydrogen or a methyl group; and R₅ is a polymethylenegroup containing from 7 to about 12 carbon atoms or a m- or p-xylylenegroup.
 25. A salt according to claim 24 wherein the anion is selectedfrom the group comprising hexafluorophosphate, tetrachlorozincate,perchlorate, hexafluoroarsenate, fluoroborate, trifluoromethylsulfonateand the halides.
 26. A salt according to claim 24 wherein M^(n+) is Co²⁺or Fe²⁺.
 27. A salt according to claim 24 wherein X and Y are each atrimethylene group.
 28. A salt according to claim 24 wherein each R₁ ishydrogen.
 29. A salt according to claim 24 wherein each R₂ is a methylgroup.
 30. A salt according to claim 24 wherein each R₄ is hydrogen, amethyl group, an n-propyl group or a benzyl group.
 31. A salt accordingto claim 24 wherein R₅ is a polymethylene group containing from 7 to 10carbon atoms.
 32. A salt according to claim 25 wherein said anion ishexafluorophosphate or chloride.
 33. A salt according to claim 32wherein X and Y are each a trimethylene group, M^(n+) is Co²⁺ or Fe²⁺each R₁ is hydrogen, each R₂ is a methyl group, each R₄ is hydrogen, amethyl group, an n-propyl group or a benzyl group and R₅ is apolymethylene group containing from 7 to 10 carbon atoms.
 34. A saltaccording to claim 1 wherein said cationic metal complex is of theformula: ##STR21## wherein: M, n⁺, R₁, R₂, R₄, X and Y are as defined inclaim 1;R is a polymethylene group containing from 4 to about 12 carbonatoms, a polymethylene group containing from 4 to about 12 carbon atomsand substituted by a methyoxycarbonyl group, or a grouping of theformula --(CH₂)_(a) --G--(CH₂)_(b) -- where a and b are eachindependently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylenegroup, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylenegroup, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfuratom, an imino group or a methylimino group, subject to the proviso thatwhen G is a sulfur atom, a imino group or a methylimino group, the sumof a and b is at least 4; and R₅ is a polymethylene group containingfrom 7 to about 12 carbon atoms or an m- or p-xylylene group.
 35. A saltaccording to claim 34 wherein the anion is selected from the groupcomprising hexafluorophosphate, tetrachlorozincate, perchlorate,hexafluoroarsenate, fluoroborate, trifluoromethylsulfonate and thehalides.
 36. A salt according to claim 34 wherein X and Y are each atrimethylene group.
 37. A salt according to claim 34 wherein each R₁ ishydrogen.
 38. A salt according to claim 34 wherein each R₂ is a methylgroup.
 39. A salt according to claim 34 wherein each R₄ is hydrogen. 40.A salt according to claim 34 wherein R₅ is a polymethylene groupcontaining from 7 to 10 carbon atoms.
 41. A salt according to claim 34wherein R is a polymethylene group containing 6 to 7 carbon atoms or anm-xylylene group.
 42. A salt according to claim 35 wherein said anion ishexafluorophosphate.
 43. A salt according to claim 42 wherein X and Yare each a trimethylene group, each R₁ is hydrogen, each R₂ is a methylgroup, each R₄ is hydrogen, R₅ is a polymethylene group containing from7 to 10 carbon atoms and R is a polymethylene group containing 6 to 7carbon atoms or an m-xylylene group.
 44. A salt according to claim 1wherein said cationic metal complex is of the formula: ##STR22##wherein: M, n⁺, R₁, R₂, R₃, X and Y are as defined in claim 1; andD is a1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene groupsubstituted by one or more methyl groups, a 9,10-anthracene group or a2,6-pyridylene group.
 45. A salt according to claim 44 wherein the anionis hexafluorophosphate, tetrachlorozincate, perchlorate,hexafluoroarsenate, fluoroborate, trifluoromethylsulfonate and thehalides.
 46. A salt according to claim 44 wherein M^(n+) is Co²⁺, Fe²⁺or Cu²⁺.
 47. A salt according to claim 44 wherein X is a trimethylenegroup or a 2-(N-methyl-2-pyridino) group.
 48. A salt according to claim44 wherein Y is a trimethylene group.
 49. A salt according to claim 44wherein each R₁ is hydrogen.
 50. A salt according to claim 44 whereineach R₂ is a methyl group.
 51. A salt according to claim 44 wherein eachR₂ is a methyl group or a phenyl group.
 52. A salt according to claim 44wherein D is a 1,3-phenylene group, a 1,4-phenylene group, atetramethylphenylene group, a 9,10-anthracene group or a 2,6-pyridylenegroup.
 53. A salt according to claim 45 wherein the anion ishexafluorophosphate or chloride.
 54. A salt according to claim 53wherein M^(n+) is Co²⁺, Fe²⁺, or Cu²⁺, X is a trimethylene group or a2-(N-methyl-2-pyridino) group, Y is a trimethylene group, each R₁ ishydrogen, each R₂ is a methyl group, each R₃ is a methyl group or aphenyl group and D is a 1,3-phenylene group, a 1,4-phenylene group, atetramethyphenylene group, a 9,10-anthracene group or a 2,6-pyridylenegroup.
 55. The salts according to claim 20 wherein M is cobalt, n is 2,X and Y are each a trimethylene group, each R₁ is hydrogen, each R₂, R₃and R₄ is a methyl group, R is a polymethylene group containing 4 to 6carbon atoms and the anion is hexafluorophosphate,namely:[(2,3,8,9,11,17-hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;[(2,3,9,10,12,18-hexamethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)]hexafluorophosphate; and[(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.
 56. The salts according to claim 20wherein M is cobalt, n is 2, X and Y are each a trimethylene group, eachR₁ is hydrogen, each R₂ and R₄ is a methyl group, each R₃ is a phenylgroup, R is a polymethylene bridge containing 4 to 6 carbon atoms andthe anion is hexafluorophosphate,namely:[(3,8,11,17-tetramethyl-2,9-diphenyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;[(3,9,12,18-tetramethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate; and[(3,10,13,19-tetramethyl-2,11-diphenyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,13,18,20,25-hexaene-κ⁴N)cobalt(II)]hexafluorophosphate.
 57. The salts according to claim 20wherein M is cobalt n is 2, X and Y are each a trimethylene group, eachR₁ and R₄ is hydrogen, each R₂ and R₃ is a methyl group, R is apentamethylene, hexamethylene, or 4-aza-methylhexamethylene group andthe anion is hexafluorophosphate,namely:[(2,10,12,18-tetramethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;[(2,11,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate; and[(2,7,12,14,20-pentamethyl-3,7,11,15,19,22,26-heptaazabicyclo[11.7.7]heptacosa-1,12,14,19,21,26-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.
 58. The salts according to claim 20wherein M is cobalt, n is 2, X and Y are each a trimethylene group, eachR₁ and R₄ is hydrogen, each R₂ is a methyl group, each R₃ is a phenylgroup, R is pentamethylene or hexamethylene and the anion ishexafluorophosphate,namely:[(12,18-dimethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate; and[(13,19-dimethyl-2,11-diphenyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.
 59. The salt according to claim 20wherein M is cobalt, n is 2, X is a 2-(N-methyl-2-pyridino)-trimethylenegroup, Y is a trimethylene group, each R₁ is hydrogen, each R₂, R₃ andR₄ is a methyl group, R is a hexamethylene group and the anion ishexafluorophosphate,namely:[(2,3,10,11,13,19-hexamethyl-23-(2-pyridyl)-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.
 60. The salt according to claim 32wherein M is cobalt, n is 2, X and Y are each a trimethylene group, eachR₁ and R₄ is hydrogen, each R₂ and R₆ is a methyl group, R₅ is aheptamethylene group and the anion is hexafluorophosphate,namely:[(12,18-dimethyl-2,10bis-methylamino-13,17,20,24-tetraazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.
 61. The salt according to claim 53wherein M is cobalt, n is 2, X and Y are each a trimethylene group, eachR₁ is hydrogen, each R₂ and R₃ is a methyl group, D is atetramethyl-1,4-phenylene group and the anion is hexafluorophosphate,namely:[(2,9,10,17,19,25,33,34-octamethyl-3,6,13,16,20,24,27,31-octaazapentacyclo[16.7.7.2⁸,11.2³,6.2¹³,16]octatriaconta-1,8,10,17,19,24,26,31,33-nonaene-κ⁴ N)cobalt(II)]hexafluorophosphate.
 62. A salt according to claim 1 dispersed in anaqueous solvent or an organic solvent which does not destroy thecomplex.
 63. An adduct of salt according to claim 1 and molecular oxygenor carbon monoxide.
 64. A salt comprising a cationic metal complex ofthe formula: ##STR23## wherein: M is Co, Fe, Cu or Mn;n+ is a positiveoxidation state of M, n being not greater than 3; X and Y are eachindependently an o-phenylene, ethylene, trimethylene,2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or2-(N-methyl-2-pyridino)-trimethylene group; each R₁ independently ishydrogen or a methyl group; each R₂ independently is hydrogen or amethyl group; each R₃ independently is hydrogen, an alkyl groupcontaining not more than about 17 carbon atoms, a benzyl group, a phenylgroup, or a phenyl group substituted by a halogen atom or by one or twomethoxy groups; or the two R₃ groups together form a carbon-carbonbridge, said carbon-carbon bridge comprising a polymethylene bridgecontaining from 7 to about 12 carbon atoms or an m- or p-xylylene group;each R₄ independently is hydrogen, an alkyl group containing not morethan about 4 carbon atoms, a cyanoalkyl group containing not more thanabout four carbon atoms, a phenyl group or a benzyl group; each R₆independently is hydrogen or a methyl group; or the two R₆ groupstogether form a nitrogen-nitrogen bridge said nitrogen-nitrogen bridgecomprising a polymethylene group containing from 4 to about 12 carbonatoms, a polymethylene group containing from 4 to about 12 carbon atomsand substituted by a methoxycarbonyl group, or a grouping of the formula--(CH₂)_(a) --G--(CH₂)_(b) -- where a and b are each independently 1, 2or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, amethoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, animino group or a methylimino group, subject to the proviso that when Gis a sulfur atom, a imino group or a methylimino group, the sum of a andb is at least 4; or the two NR₄ R₆ groups together form a bis-piperazinobridge of the formula: ##STR24## where D is a 1,3-phenylene group, a1,4-phenylene group, a 1,4-phenylene group substituted by one or moremethyl groups, a 9,10-anthracene group or a 2,6-pyridylene group,subject to the proviso that when the two R₃ groups do not form acarbon-carbon bridge, either the two R₆ groups must form anitrogen-nitrogen bridge or the two NR₄ R₆ groups must form abis-piperazino bridge; and Z is an electron donor selected from thegroup consisting of the halide ions, cyanate, thiocyanate, azide,acetonitrile, water, an alkanol containing not more than about fivecarbon atoms, pyridine, 4-aminopyridine, imidazole andN-methylimidazole.
 65. A salt according to claim 64 wherein the anion isselected from the group comprising hexafluorophosphate,tetrachlorozincate, perchlorate, hexafluoroarsenate, fluoroborate,trifluoromethylsulfonate and the halides.
 66. A salt according to claim64 wherein M^(n+) is Co²⁺, Co³⁺, Fe²⁺, Fe³⁺, Cu²⁺, Mn²⁺, or Mn³⁺.
 67. Asalt according to claim 64 wherein X and Y are each a trimethylenegroup.
 68. A salt according to claim 64 wherein each R₁ is hydrogen. 69.A salt according to claim 64 wherein each R₂ is a methyl group.
 70. Asalt according to claim 64 wherein R₃ is hydrogen, a methyl group, aphenyl group, a t-butyl group, an n-heptyl group, an n-heptadecyl groupa 4-methoxyphenyl group, a 4-chlorophenyl group, a 4-fluorophenyl groupor a 3,5-dimethoxyphenyl group, or the two R₃ groups together form apolymethylene group containing 7 to 12 carbon atoms or a m-xylylenegroup.
 71. A salt according to claim 64 wherein R₄ is hydrogen, a methylgroup, an n-propyl group or a benzyl group.
 72. A salt according toclaim 64 wherein the two R₆ groups together form a nitrogen-nitrogenbridge, said nitrogen bridge comprising a polymethylene bridge of 4 toabout 8 carbon atoms, an m- or p-xylylene group or a --(CH₂)₃--(9,9-flourylene)--(CH₂)₃ -- group.
 73. A salt according to claim 65wherein said anion is hexafluorophosphate or chloride.
 74. A saltaccording to claim 64 wherein said cationic metal complex is of theformula: ##STR25## wherein: M, n+, R₁, R₂, R₄, X, Y and Z are as definedin claim 64; each R₃ independently is hydrogen, an alkyl groupcontaining not more than about 17 carbon atoms, a benzyl group, a phenylgroup, or a phenyl group substituted by a halogen atom or by one or twomethoxy groups;R is a polymethylene group containing from 4 to about 12carbon atoms, a polymethylene group containing from 4 to about 12 carbonatoms and substituted by a methoxycarbonyl group, or a grouping of theformula --(CH₂)_(a) --G--(CH₂)_(b) -- where a and b are eachindependently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylenegroup, a methoxy-substituted 1,4-phenylene group, a 9,9- fluorylenegroup, a 1,3-cyclohexylene group, a 1,4- cyclohexylene group, a sulfuratom, an imino group or a methylimino group, subject to the proviso thatwhen G is a sulfur atom, a imino group or a methylimino group, the sumof a and b is at least
 4. 75. A salt according to claim 74 wherein theanion is selected from the group comprising hexafluorophosphate,tetrachlorozincate, perchlorate, hexafluoroarsenate, fluoroborate,trifluoromethylsulfonate and the halides.
 76. A salt according to claim74 wherein M^(n+) is Co²⁺, Co³⁺, Fe²⁺, Fe³⁺, Cu²⁺, Mn²⁺ or Mn³⁺.
 77. Asalt according to claim 74 wherein X and Y are each a trimethylenegroup.
 78. A salt according to claim 74 wherein each R₁ is hydrogen. 79.A salt according to claim 74 wherein each R₂ is a methyl group.
 80. Asalt according to claim 74 wherein each R₃ is hydrogen, a methyl group,a phenyl group, a t-butyl group, an n-heptyl group, a 4-methoxyphenylgroup, a 4-chlorophenyl group, a 4-fluorophenyl group or a3,5-dimethoxyphenyl group.
 81. A salt according to claim 74 wherein eachR₄ is hydrogen, a methyl group or a benzyl group.
 82. A salt accordingto claim 74 wherein R is a polymethylene bridge of 4 to about 8 carbonatoms, an m- or p-xylylene group or a --(CH₂)₃--(9,9-flourylene)--(CH₂)₂)₃ -- group.
 83. A salt according to claim 74wherein Z is chloride, cyanate, thiocyanate, azide, ethanol,acetonitrile, pyridine, 4-aminopyridine, imidazole or N-methylimidazole.84. A salt according to claim 75 wherein said anion ishexafluorophosphate or chloride.
 85. A salt according to claim 84wherein M^(n+) is Co²⁺, Co³⁺, Fe²⁺, Fe³⁺, Mn²⁺, Mn³⁺ or Cu²⁺, X and Yare each a trimethylene group, each R₁ is hydrogen, each R₂ is a methylgroup, each R₃ is hydrogen, a methyl group, a phenyl group, a t-butylgroup, an n-heptyl group, a 4-methoxyphenyl group, a 4-chlorophenylgroup, a 4-fluorophenyl group or a 3,5-dimethoxyphenyl group, each R₄ ishydrogen, a methyl group or a benzyl group, R is a polymethylene bridgeof 4 to about 8 carbon atoms, an m- or p-xylylene group or a --(CH₂)₃--(9,9-fluorylene)--(CH₂)₃ -- group and Z is chloride, cyanate,thiocyanate, azide, ethanol, acetonitrile, pyridine, 4-aminopyridine,imidazole or N-methylimidazole.
 86. A salt according to claim 64 whereinsaid cationic metal complex of the formula: ##STR26## wherein M, n⁺, R₁,R₂, X, Y and Z are as defined in claim 64;each R₄ independently ishydrogen; an alkyl group containing not more than about 4 carbon atomsor benzyl; each R₆ independently is hydrogen or a methyl group; and R₅is a polymethylene group containing from about 7 to about 12 carbonatoms or a m- or p-xylylene group.
 87. A salt according to claim 86wherein the anion is selected from the group comprisinghexafluorophosphate, tetrachlorozincate, perchlorate,hexafluoroarsenate, fluoroborate, trifluoromethylsulfonate and thehalides.
 88. A salt according to claim 86 wherein M is cobalt or iron, nis 2, each R₁ is hydrogen, each R₂ and R₄ is hydrogen or a methyl group,each R₃ is hydrogen, a methyl group, an ethyl group, a n-propyl group ora benzyl group, X and Y are each a trimethylene group, R₅ is apolymethylene group containing 7 to 12 carbon atoms, Z is chloride,acetonitrile, or water and said anion is hexafluorophosphate.
 89. A saltaccording to claim 64 wherein said cationic metal complex is of theformula: ##STR27## wherein M, n³⁰ , R₁, R₂, R₄, X, Y and Z are asdefined in claim 64;R is a polymethylene group containing from 4 toabout 12 carbon atoms, a polymethylene group containing from 4 to about12 carbon atoms and substituted by a methoxycarbonyl group, or agrouping of the formula --(CH₂)_(a) --G--(CH₂)_(b) -- where a and b areeach independently 1, 2 or 3 and G is a 1,3-phenylene group, a1,4-phenylene group, a methoxy-substituted 1,4-phenylene group, a9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylanegroup, a sulfur atom, an imino group or a methylimino group, subject tothe proviso that when G is a sulfur atom, a imino group or a methyliminogroup, the sum of a and b is at least 4; and R₅ is a polymethylene groupcontaining from 7 to about 12 carbon atoms or an m- or p-xylylene group.90. A salt according to claim 89 wherein the anion is selected from thegroup comprising hexafluorophosphate, tetrachlorozincate, perchlorate,hexafluoroarsenate, fluoroborate, trifluoromethylsulfonate and thehalides.
 91. A salt according to claim 64 wherein said cationic metalcomplex is of the formula: ##STR28## wherein M, n⁺, R₁, R₂, R₃, X, Y andZ are as defined in claim 64; andD is a 1,3-phenylene group, a1,4-phenylene group, a 1,4-phenylene group substituted by one or moremethyl groups, a 9,10-anthracene group or a 2,6-pyridylene group.
 92. Asalt according to claim 91 wherein the anion is selected from the groupcomprising hexafluorophosphate, tetrachlorozincate, perchlorate,hexafluoroarsenate, fluoroborate, trifluoromethylsulfonate and thehalides.
 93. A salt according to claim 91 wherein M^(n+) is Co²⁺ orFe²⁺.
 94. A salt according to claim 91 wherein X and Y are each atrimethylene group.
 95. A salt according to claim 91 wherein each R₁ ishydrogen.
 96. A salt according to claim 91 wherein each R₂ is a methylgroup.
 97. A salt according to claim 91 wherein each R₃ is a methylgroup.
 98. A salt according to claim 91 wherein each D is a1,3-phenylene group, a tetramethyl-1,4-phenylene group or a9,10-anthracene group
 99. A salt according to claim 91 where Z ismethanol, chloride or water.
 100. A salt according to claim 92 whereinsaid anion is said hexafluorophosphate.
 101. A salt according to claim100, wherein each R₁ is hydrogen , each R₂ and R₃ is a methyl group, Dis a 1,3-phenylene group, a tetramethyl-1,4-phenylene group or a9,10-anthracene group and Z is methanol, chloride or water.
 102. Thesalts according to claim 75 wherein M is iron, n is 2, X and Y are eacha trimethylene group, each R₁ is hydrogen, each R₂ is a methyl group,each R₃ is a p-methoxypheny, p-chlorophenyl, p-fluorophenyl, n-heptyl ormethyl group, each R₄ is a methyl group, R is m-xylylene, Z is chlorideand the anion is hexafluorophosphate,namely:[chloro(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[chloro(2,12-di-n-heptyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[chloro(2,12-di-p-methoxyphenyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[chloro(2,12-di-p-chlorophenyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate; and[chloro(2,12-di-p-fluorophenyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate.
 103. The salt according to claim 75 wherein M iscobalt, n is 2, X and Y are each a trimethylene group, each R₁ ishydrogen, each R₂ is a methyl group, R is a phenyl group, each R₄ ishydrogen, R is a m-xylylene group, Z is acetonitrile and the anion ishexafluorophosphate,namely:[acetonitrile(14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa- 1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)cobalt(II)]hexafluorophosphate.
 104. The salts according to claim 75 wherein M isiron, n is 2, X and Y are each a trimethylene group, each R₁ ishydrogen, each R₂ is a methyl group, each R₃ is a methyl group, each R₄is a methyl or benzyl group, R is a m-xylylene group, Z is acetonitrileand the anion is hexafluorophosphatenamely:[acetonitrile(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate; and[acetonitrile(3,11-dibenzyl-2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate.
 105. The salts according to claim 75 wherein M isiron, n is 2, X and Y are each a trimethylene group, each R₁ ishydrogen, each R₂ is a methyl group, each R₃ is a phenyl group, each R₄is a methyl or benzyl group, R is a m-xylylene group, Z is acetonitriteand the anion is hexafluorophosphate,namely:[acetonitrile(3,11,14,20-tetramethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate; and[acetonitrile(3,11-dibenzyl-14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate.
 106. The salts according to claim 75 wherein M iscobalt, n is 2, X and Y are each a trimethylene group, each R₁ ishydrogen, each R₂ and R₃ is a methyl group, each R₄ is hydrogen, R is aheptamethylene or m-xylylene group, Z is acetonitrile and the anion ishexafluorophosphate,namely:[acetonitrile(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazabicyclo[11.7.7]heptacosa-1,12,14,19,21,26-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate; and[acetonitrile(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)cobalt(II)]hexafluorophosphate.
 107. The salt according to claim 75 wherein M iscobalt, n is 2, X and Y are each a trimethylene group, each R₁ ishydrogen, each R₂ is a methyl group, each R₃ is hydrogen, each R₄ is amethyl group, R is a hexamethylene group, Z is acetonitrile and theanion is hexafluorophosphate,namely:[acetonitrile(3,10,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.
 108. The salts according to claim 87wherein M is iron, n is 2, X and Y are each a trimethylene group, eachR₁ is hydrogen, each R₂, R₄ and R₆ is a methyl group, R₅ is aheptamethylene or octamethylene group, Z is chloride and the anion ishexafluorophosphate,namely:[chloro(2,10-bis-dimethylamino-12,18-dimethyl-13,17,20,24-tetraazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)iron(II)] hexafluorophosphate; and[chloro(2,11-bis-dimethylamino-13,19-dimethyl-14,18,21,25-tetraazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)iron(II)] hexafluorophosphate.
 109. The salt according to claim 87where M is cobalt, n is 2, X and Y are each a trimethylene group, eachR₁ is hydrogen, each R₂ is a methyl group, each R₄ is a n-propyl, R₆ ishydrogen, R₅ is a heptamethylene group, Z is acetonitrile and the anionis hexafluorophosphate,namely:[acetonitrile(12,18-dimethyl-2,10-bis-propylamino-13,17,20,24-tetraazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.
 110. The salt according to claim 87wherein M is cobalt, n is 2, X and Y are each a trimethylene group, eachR₁ is hydrogen, each R₂, R₄ and R₆ is a methyl group, R₅ is anoctamethylene group, Z is acetonitrile and the anion ishexafluorophosphate,namely:[acetonitrile(2,11-bis-dimethylamino-13,19-dimethyl-14,18,21,25-tetraazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.
 111. A salt according to claim 64dispersed in an aqueous solvent or an organic solvent which does notdestroy the complex.
 112. An adduct of a salt according to claim 64 andmolecular oxygen or carbon monoxide.
 113. A salt comprising a cationicmetal complex of the formula: ##STR29## wherein: M^(n+) is Ni²⁺ ;X and Yare each independently an o-phenylene, ethylene, trimethylene,2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or2-(N-methyl-2-pyridino)-trimethylene group; each R₁ independently ishydrogen or a methyl group; each R₂ independently is hydrogen or amethyl group; each R₄ independently is hydrogen, an alkyl groupcontaining not more than about 4 carbon atoms, a cyanoalkyl groupcontaining not more than about four carbon atoms, a phenyl group or abenzyl group; each R₆ independently is hydrogen or a methyl group; andR₅ is a polymethylene group containing from about 7 to about 12 carbonatoms or a m- or p-xylylene group.
 114. A salt according to claim 113wherein the anion is selected from the group comprisinghexafluorophosphate, tetrachlorozincate, perchlorate,hexafluoroarsenate, fluoroborate, trifluoromethylsulfonate and thehalides.
 115. A salt comprising a cationic metal complex of the formula:##STR30## wherein: M^(n+) is Ni²⁺ ;X and Y are each independently ano-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene,2-methyl substituted trimethylene or2-(N-methyl-2-pyridino)-trimethylene group; each R₁ independently ishydrogen or a methyl group; each R₂ independently is hydrogen or amethyl group; each R₄ independently is hydrogen, an alkyl groupcontaining not more than about 4 carbon atoms, a cyanoalkyl groupcontaining not more than about four carbon atoms, a phenyl group or abenzyl group; R is a polymethylene group containing from 4 to about 12carbon atoms, a polymethylene group containing from 4 to about 12 carbonatoms and substituted by a methyoxycarbonyl group, or a grouping of theformula --(CH₂)_(a) --G--(CH₂)_(b) --where a and b are eachindependently 1, 2 or 3 G is a 1,3-phenylene group, a 1,4-phenylenegroup, a methoxy-substituted 1,4-phenylene group, a 9,9-fluorylenegroup, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfuratom, an imino group or a methylimino group, subject to the proviso thatwhen G is a sulfur atom, a imino group or a methylimino group, the sumof a and b is at least 4; and R₅ is a polymethylene group containingfrom 7 to about 12 carbon atoms or an m- or p-xylylene group.
 116. Asalt according to claim 115 wherein the anion is selected from the groupcomprising hexafluorophosphate, tetrachlorozincate, perchlorate,hexafluoroarsenate, fluoroborate, trifluoromethylsulfonate and thehalides.
 117. A salt comprising a cationic metal complex of the formula:##STR31## wherein: M^(n+) is Ni²⁺ ;X and Y are each independently ano-phenylene, ethylene, trimethylene, 2-(2-pyridyl)-trimethylene or2-(N-methyl-2-pyridino)-trimethylene group; each R₁ independently ishydrogen or a methyl group; each R₂ independently is hydrogen or amethyl group; each R₃ independently is hydrogen, an alkyl groupcontaining not more than about 17 carbon atoms, a benzyl group, a phenylgroup, or a phenyl group substituted by a halogen atom or by one or twomethoxy groups; or the two R₃ groups together form a carbon-carbonbridge, said carbon-carbon bridge comprising a polymethylene bridgecontaining from 7 to about 12 carbon atoms or an m- or p-xylylene group;and D is a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylenegroup substituted by one or more methyl groups, a 9,10-anthracene groupor a 2,6-pyridylene group.
 118. A salt according to claim 117 whereinthe anion is selected from the group comprising hexafluorophosphate,tetrachlorozincate, perchlorate, hexafluoroarsenate, fluoroborate,trifluormethylsulfonate and the halides.
 119. A method for removingmolecular oxygen from a gaseous mixture which comprises:exposing a saltof the formula: ##STR32## wherein: M is Co, Fe, Cu or Mn; n⁺ is apositive oxidation state of M, n being not greater than 3; X and Y areeach independently an o-phenylene, ethylene, trimethylene,2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or2-(N-methyl-2-pyridino)-trimethylene group; each R₁ independently ishydrogen or a methyl group; each R₂ independently is hydrogen or amethyl group; each R₃ independently is hydrogen, an alkyl groupcontaining not more than about 17 carbon atoms, a benzyl group, a phenylgroup, or a phenyl group substituted by a halogen atom or by one or twomethoxy groups; or the two R₃ groups together form a carbon-carbonbridge, said carbon-carbon bridge comprising a polymethylene bridgecontaining from 7 to about 12 carbon atoms or an m- or p-xylylene group;each R₄ independently is hydrogen, an alkyl group containing not morethan about 4 carbon atoms, a cyanoalkyl group containing not more thanabout four carbon atoms, a phenyl group or a benzyl group; each R₆independently is hydrogen or a methyl group; or the two R₆ groupstogether form a nitrogen-nitrogen bridge, said nitrogen-nitrogen bridgecomprising a polymethylene group containing from 4 to about 12 carbonatoms, a polymethylene group containing from 4 to about 12 carbon atomsand substituted by a methoxycarbonyl group, or a grouping of theformula:

    --(CH.sub.2).sub.1 --G--(CH.sub.2).sub.b --

where a and b are each independently 1, 2 or 3 and G is a 1,3-phenylenegroup, a 1, 4-phenylene group, a methoxy-substituted 1,4-phenylenegroup, a 9,9-fluorylene group, a 1,3-cyclohexylene group, a1,4-cyclohexylene group, a sulfur atom, an imino group, or a methyliminogroup, subject to the proviso that when G is a sulfur atom, a iminogroup or a methylimino group, the sum of a and b is at least 4; or thetwo NR₄ R₆ groups together form a bis-piperazino bridge of the formula##STR33## where D is a 1,3-phenylene group, a 1,4-phenylene group, a1,4-phenylene group substituted by one or more methyl groups, a9,10-anthracene group or a 2,6-pyridylene group, subject to the provisothat when the two R₃ groups do not form a carbon-carbon bridge, eitherthe two R₆ groups must form a nitrogen-nitrogen bridge or the two NR₄ R₆groups must form a bis-piperazino group, to said mixture therebyallowing said cationic metal complex to complex molecular oxygen andthus to absorb oxygen from said gaseous mixture.
 120. A method accordingto claim 119 wherein, after said cationic metal complex has complexedoxygen, and salt is withdrawn from contact with said gaseous mixture andis placed in a second environment wherein the oxygen partial pressure isless than the pressure in equilibrium with the oxygenated form of saidsalt under the conditions in said second environment, thereby allowingsaid cationic metal complex to decomplex molecular oxygen and therebyrelease oxygen into said second environment.
 121. A method according toclaim 120 wherein said oxygen partial pressure in said secondenvironment is lower than the oxygen partial pressure in said firstenvironment.
 122. A method according to claim 121 wherein said firstenvironment comprises the lungs of a mammal and said second environmentcomprises the non-lung tissues of said mammal.
 123. A method accordingto claim 120 wherein said second environment is at a higher temperaturethan said first environment.
 124. A method according to claim 120wherein said saltcomprises:[(2,3,8,9,11,17-hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(2,3,9,10,12,18-hexamethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]-pentacosa-1,10,12,17,19,24-hexaene-κ⁴ N)cobalt(II)]hexafluorophosphate;[(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(3,8,11,17-tetramethyl-2,9-diphenyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;[(3,9,12,18-tetramethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,17,19,24-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(3,10,13,19-tetramethyl-2,11-diphenyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,1118,20,25-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(2,10,12,18-tetramethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(2,11,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(2,7,12,14,20-pentamethyl-3,7,11,15,19,22,26-heptaazabicyclo[11.7.7]heptacosa-1,12,14,19,21,26-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(12,18-dimethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[13,19-dimethyl-2,11-diphenyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(2,3,10,11,13,19-hexamethyl-23-(2-pyridyl)-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;[(12,18-dimethyl-2,10-bis-methylamino-13,17,20,24-tetraazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate; or[(2,9,10,17,19,25,33,34-octamethyl-3,6,13,16,20,24,27,31-octaazapentacyclo[16.7.7.2⁸,11.2³,6.2¹³,16]octatriaconta-1,8,10,17,19,24,26,31,33-nonaene-κ⁴ N)cobalt(II)]hexafluorophosphate.
 125. A method for removing molecular oxygen from agaseous mixture, which comprises:exposing a salt of the formula:##STR34## wherein: M is Co, Fe, Cu or Mn; n⁺ is a positive oxidationstate of M, n being not greater than 3; X and Y are each independentlyan o-phenylene, ethylene, trimethylene 2-(2-pyridyl)-trimethylene or2-(N-methyl-2-pyridino)-trimethylene group; each R₁ independently ishydrogen or a methyl group; each R₂ independently is hydrogen or amethyl group; each R₃ independently is hydrogen, an alkyl groupcontaining not more than about 17 carbon atoms, a benzyl group, a phenylgroup, or a phenyl group substituted by a halogen atom or by one or twomethoxy groups; or the two R₃ groups together form a carbon-carbonbridge, said carbon-carbon bridge comprising a polymethylene bridgecontaining from 7 to about 12 carbon atoms or an m- or p-xylylene group;each R₄ independently is hydrogen, an alkyl group containing not morethan about 4 carbon atoms, a cyanoalkyl group containing not more thanabout four carbon atoms, a phenyl group or a benzyl group; each R₆independently is hydrogen or a methyl group; or the two R₆ groupstogether form a nitrogen-nitrogen bridge said nitrogen-nitrogen bridgecomprising a polymethylene group containing from 4 to about 12 carbonatoms, a polymethylene group containing from 4 to about 12 carbon atomsand substituted by a methoxycarbonyl group, or a grouping of the formula--(CH₂)_(a) --G--(CH₂)_(b) --where a and b are each independently 1, 2or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, amethoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, animino group or a methylimino group, subject to the proviso that when Gis a sulfur atom, a imino group or a methylimino group, the sum of a andb is at least 4; or the two NR₄ R₆ groups together form a bis-piperazinobridge of the formula: ##STR35## where D is a 1,3-phenylene group, a1,4-phenylene group, a 1,4-phenylene group substituted by one or moremethyl groups, a 9,10-anthracene group or a 2,6-pyridylene group,subject to the proviso that when the two R₃ groups do not form acarbon-carbon bridge, either the two R₆ groups must form anitrogen-nitrogen bridge or the two NR₄ R₆ groups must form abis-piperazino group; and Z is an electron donor selected from the groupconsisting of the halide ions, cyanate, thiocyanate, azide,acetonitrile, water, an alkanol containing not more than about fivecarbon atoms, pyridine, 4-aminopyridine, imidazole andN-methylimidazole, to said mixture thereby allowing said cationic metalcomplex to complex molecular oxygen and thus to absorb oxygen from saidgaseous mixture.
 126. A method according to claim 125 wherein, aftersaid cationic metal complex has complexed oxygen, said salt is withdrawnfrom contact with said gaseous mixture and is placed in a secondenvironment wherein the oxygen partial pressure is less than the oxygenpressure in equilibrium with the oxygenated form of said salt under theconditions in said second environment, thereby allowing said cationicmetal complex to decomplex molecular oxygen and thereby release oxygeninto said second environment.
 127. A method according to claim 126wherein said oxygen partial pressure in said second environment is lowerthan the oxygen partial pressure in said first environment.
 128. Amethod according to claim 127 wherein said first environment comprisesthe lungs of a mammal and said second environment comprises the non-lungtissues of said mammal.
 129. A method according to claim 126 whereinsaid second environment is at a higher temperature than said firstenvironment.
 130. A method according to claim 125 wherein said saltcomprises:[chloro(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ Niron(II)]hexafluorophosphate;[chloro(2,12-di-n-heptyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo-[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[chloro(2,12-di-p-methoxyphenyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7.9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[chloro(2,12-di-p-chlorophenyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[chloro(2,12-di-p-fluorophenyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[acetonitrile(14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)cobalt(II)]hexafluorophosphate;[acetonitrile(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[acetonitrile(3,11-dibenzyl-2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[acetonitrile(3,11,14,20-tetramethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9 ]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[acetonitrile(3,11-dibenzyl-14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[acetonitrile(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazabicyclo[11.7.7]heptacosa-1,12,14,19,21,26-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;[acetonitrile(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)cobalt(II)]hexafluorophosphate;[acetonitrile(3,10,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;[chloro(2,10-bis-dimethylamino-12,18-dimethyl-13,17,20,24-tetraazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)iron(II)] hexafluorophosphate;[chloro(2,11-bis-dimethylamino-13,19-dimethyl-14,18,21,25-tetraazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)iron(II)] hexafluorophosphate;[acetonitrile(12,18-dimethyl-2,10-bis-propylamino-13,17,20,24-tetraazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate; or[acetonitrile(2,11-bis-dimethylamino-13,19-dimethyl-14,18,21,25-tetraazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.
 131. In a method for increasing theproportion of a molecular oxygen in a gaseous mixture, whichcomprises:passing said gaseous mixture over one face of an immobilizedliquid membrane containing an oxygen-complexing compound; allowingmolecular oxygen to diffuse selectively through said liquid membrane;removing from adjacent the opposed face of said liquid membrane anoxygen-enriched gas containing a higher proportion of molecular oxygenthan said gaseous mixture, the improvement which comprises using as saidliquid membrane a liquid membrane containing a solution of saltcomprising a cationic metal complex of the formula: ##STR36## wherein Mis Co, Fe, Cu or Mn; n⁺ is a positive oxidation state of M, n being notgreater than 3; X and Y are each independently an o-phenylene, ethylene,trimethylene, 2-(2-pyridyl)-trimethylene, 2-methyl substitutedtrimethylene, or 2-(N-methyl-2-pyridino)-trimethylene group; each R₁independently is hydrogen or a methyl group; each R₂ independently ishydrogen or a methyl group; each R₃ independently is hydrogen, an alkylgroup consisting not more than about 17 carbon atoms, a benzyl group, aphenyl group, or a phenyl group substituted by a halogen atom or by oneor two methoxy groups; or the two R₃ groups together form acarbon-carbon bridge, said carbon-carbon bridge comprising apolymethylene bridge containing from 7 to about 12 carbon atoms or an m-or p-xylylene group; each R₄ independently is hydrogen, an alkyl groupcontaining not more than about 4 carbon atoms, a cyanoalkyl groupcontaining not more than about four carbon atoms, a phenyl group or abenzyl group; each R₆ independently is hydrogen or a methyl group; orthe two R₆ groups together form a nitrogen-nitrogen bridge, saidnitrogen-nitrogen bridge comprising a polymethylene group containingfrom 4 to about 12 carbon atoms, a polymethylene group containing from 4to about 12 carbon atoms and substituted by a methoxycarbonyl group, ora grouping of the formula:

    --(CH.sub.2).sub.a --G--(CH.sub.2).sub.b --

where a and b are each independently 1,2, or 3 and G is a 1,3-phenylenegroup, a 1,4-phenylene group, a methoxy-substituted 1,4-phenylene group,a 9,9-fluorylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylenegroup, a sulfur atom, an imino group, or a methylimino group subject tothe proviso that when G is a sulfur atom, a imino group or a methyliminogroup, the sum of a and b is at least 4; or the two NR₄ R₆ groupstogether form a bis-piperazino bridge of the formula: ##STR37## where Dis a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-phenylene groupsubstituted by one or more methyl groups, a 9,10-anthracene group or a2,6-pyridylene group, subject to the proviso that when the two R₃ groupsdo not form a carbon-carbon bridge, either the two R₆ groups must form anitrogen-nitrogen bridge or the two NR₄ R₆ groups must form abis-piperazino bridge.
 132. A method according to claim 131 wherein saidsaltcomprises:[(2,3,8,9,11,17-hexamethyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(2,3,9,10,12,18-hexamethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]-pentacosa-1,10,12,17,19,24-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(2,3,10,11,13,19-hexamethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(3,8,11,17-tetramethyl-2,9-diphenyl-3,8,12,16,19,23-hexaazabicyclo[8.7.7]tetracosa-1,9,11,16,18,23-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;[(3,9,12,18-tetramethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-78 ⁴ N)cobalt(II)] hexafluorophosphate;[(3,10,13,19-tetramethyl-2,11-diphenyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(2,10,12,18-tetramethyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(2,11,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(2,7,12,14,20-pentamethyl-3,7,11,15,19,22,26-heptaazabicyclo[11.7.7]heptacosa-1,12,14,19,21,26-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(12,18-dimethyl-2,10-diphenyl-3,9,13,17,20,24-hexaazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(13,19-dimethyl-2,11-diphenyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴ N)cobalt(II)] hexafluorophosphate;[(2,3,10,11,13,19-hexamethyl-23-(2-pyridyl)-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;[(12,18-dimethyl-2,10-bis-methylamino-13,17,20,24-tetraazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate; or[(2,9,10,17,19,25,33,34-octamethyl-3,6,13,16,20,24,27,31-octaazapentacyclo[16.7.7.2⁸,11.1³,6.2¹³,16]octatriaconta-1,8,10,17,19,24,26,31,33-nonaene-κ⁴ N)cobalt(II)]hexafluorophosphate.
 133. In a method for increasing the proportion of amolecular oxygen in a gaseous mixture, which comprises:passing saidgaseous mixture over one face of an immobilized liquid membranecontaining an oxygen-complexing compound; allowing molecular oxygen todiffuse selectively through said liquid membrane; removing from adjacentthe opposed face of said liquid membrane an oxygen-enriched gascontaining a higher proportion of molecular oxygen than said gaseousmixture, the improvement which comprises using as said liquid membrane aliquid membrane containing a solution of a salt comprising a cationicmetal complex of the formula: ##STR38## wherein: M is Co, Fe, Cu or Mn;n⁺ is a positive oxidation state of M, n being not greater than 3; X andY are each independently an o-phenylene, ethylene, trimethylene,2-(2-pyridyl)-trimethylene, 2-methyl substituted trimethylene or2-(N-methyl-2-pyridino)-trimethylene group; each R₁ independently ishydrogen or a methyl group; each R₂ independently is hydrogen or amethyl group; each R₃ independently is hydrogen, an alkyl groupcontaining not more than about 17 carbon atoms, a benzyl group, a phenylgroup, or a phenyul group substituted by a halogen atom or by one or twomethoxy groups; or the two R₃ groups together form a carbon-carbonbridge, said carbon-carbon bridge comprising a polymethylene bridgecontaining from 7 to about 12 carbon atoms or an m- or p-xylylene group;each R₄ independently is hydrogen, an alkyl group containing not morethan about four carbon atoms, a phenyl group or a benzyl group; R₆independently is hydrogen or a methyl group, or the two R₆ groupstogether form a nitrogen-nitrogen bridge said nitrogen-nitrogen bridgecomprising a polymethylene group containing from 4 to about 12 carbonatoms, a polymethylene group containing from 4 to about 12 carbon atomsand substituted by a methoxycarbonyl group, or a grouping of the formula--(CH₂)_(a) --G--(CH₂)_(b) --where a and b are each independently 1, 2or 3 and G is a 1,3-phenylene group, a 1,4-phenylene group, amethoxy-substituted 1,4-phenylene group, a 9,9-fluorylene group, a1,3-cyclohexylene group, a 1,4-cyclohexylene group, a sulfur atom, aimino group or a methylimino group, the sum of a and b is at least 4; orthe two NR₄ R₆ groups together form a bis-piperazino bridge of theformula: ##STR39## where D is a 1,3-phenylene group, a 1,4-phenylenegroup, a 1,4-phenylene group substituted by one or more methyl groups, a9,10-anthracene group or a 2,6-pyridylene group subject to the provisothat when the two R₃ groups do not form a carbon-carbon bridge, eitherthe two R₆ groups must form a nitrogen-nitrogen bridge or the two NR₄ R₆groups must form a bis-piperazino bridge; and Z is an electron donorselected from the group consisting of the halide ions, cyanate,thiocyanate, azide, acetonitrile, water, an alkanol containing not morethan about five carbon atoms, pyridine, 4-aminopyridine, imidazole andN-methylimidazole.
 134. A method according to claim 133 wherein saidsaltcomprises:[chloro(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[chloro(2,12-di-n-heptyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo-[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[chloro(2,12-di-p-methoxyphenyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[chloro(2,12-di-p-chlorophenyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[chloro(2,12-di-p-fluorophenyl-3,11,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[acetonitrile(14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)cobalt(II)]hexafluorophosphate;[acetonitrile(2,3,11,12,14,20-hexamethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate; [acetonitrile(3,11-dibenzyl-2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[acetonitrile(3,11,14,20-tetramethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[acetonitrile(3,11-dibenzyl-14,20-dimethyl-2,12-diphenyl-3,11,15,19,22,26-hexaazatricyclo[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)iron(II)]hexafluorophosphate;[acetonitrile(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazabicyclo[11.7.7]heptacosa-1,12,14,19,21,26-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;[acetonitrile(2,12,14,20-tetramethyl-3,11,15,19,22,26-hexaazatricyclo-[11.7.7.1⁵,9]octacosa-1,5,7,9(28),12,14,19,21,26-nonaene-κ⁴ N)cobalt(II)]hexafluorophosphate;[acetonitrile(3,10,13,19-tetramethyl-3,10,14,18,21,25-hexaazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate;[chloro(2,10-bis-dimethylamino-12,18-dimethyl-13,17,20,24-tetraazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)iron(II)] hexafluorophosphate;[chloro(2,11-bis-dimethylamino13,19dimethyl-14,18,21,25-tetraazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)iron(II)] hexafluorophosphate;[acetonitrile(12,18-dimethyl-2,10-bis-propylamino-13,17,20,24-tetraazabicyclo[9.7.7]pentacosa-1,10,12,17,19,24-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate; or[acetonitrile(2,11-bis-dimethylamino-13,19-dimethyl-14,18,21,25-tetraazabicyclo[10.7.7]hexacosa-1,11,13,18,20,25-hexaene-κ⁴N)cobalt(II)] hexafluorophosphate.
 135. A process for the separation andpurification of oxygen and nitrogen comprising:(a) bringing anatmospheric air feed stream into contact with a solution containing asolvent or solvent mixture, an axial base and an oxygen carrier, saidsolvent or solvent mixture being capable of dissolving the axial baseand the oxygen carrier when they are present together, when they arepresent together, said axial base being capable of providing acoordinating atom to the oxygen carrier, and said oxygen carrier being ametal-containing complex which is a salt of a cation having thestructure ##STR40## wherein:M is a metal selected from cobalt, iron,copper, nickel, manganese, ruthenium or rhodium; n⁺ is a positiveoxidation state of M, n being not greater than 3; each R₁ independentlyis hydrogen or a methyl group; each R₂ independently is hydrogen or amethyl group; each R₃ independently is hydrogen, an alkyl groupcontaining not more than about 17 carbon atoms, a benzyl group, a phenylgroup, or a phenyl group substituted by a halogen atom or by one or twomethoxy groups; each R₄ independently is hydrogen, an alkyl groupcontaining not more than about 4 carbon atoms, a cyanoalkyl groupcontaining not more than about 4 carbon atoms, a phenyl group or abenzyl group; R is a polymethylene group containing from about 4 toabout 12 carbon atoms, or a grouping of the formula --(CH₂)_(a)--G--(CH₂)_(b) --where a and b are each independently 1, 2 or 3 and G isa 1,3-phenylene group, a 1,4-phenylene group, amethoxy-substituted-1,4-phenylene group, a 9,9-fluorylene group, animino group or a methylimino group, subject to the proviso that, when Gis an imino group or a methylimino group, the sum of a and b is at least4; and X and Y are each independently an o-phenylene, ethylene,trimethylene, 2-(2-pyridyl)-trimethylene,2-methyl-substituted-trimethylene or 2-(N-methyl-2-2pyridino)-trimethylene group, said solution adsorbing oxygen from saidatmospheric air feed stream; (b) collecting nitrogen from theatmospheric air feed stream after the oxygen has been adsorbed; (c)desorbing oxygen from said solution to a gaseous product stream; and (d)collecting oxygen from the product stream after the oxygen has beendesorbed.
 136. A process for the separation and purification of oxygencomprising:(a) bringing a gaseous, oxygen-containing feed stream intocontact with a solution containing a solvent or solvent mixture, anaxial base and an oxygen carrier, said solvent mixture being capable ofdissolving the axial base and the oxygen carrier when they are presenttogether, said axial base being capable of providing a coordinating atomto the oxygen carrier, and said oxygen carrier being a metal-containingcomplex which is a salt of a cation having the formula ##STR41##wherein: M is a metal selected from cobalt, iron, copper, nickel,manganese, ruthenium or rhodium;n⁺ is a positive oxidation state of M, nbeing not greater than 3; each R₁ independently is hydrogen or a methylgroup; each R₂ independently is hydrogen or a methyl group; each R₃independently is hydrogen, an alkyl group containing not more than about17 carbon atoms, a benzyl group, a phenyl group, or a phenyl groupsubstituted by a halogen atom or by one or two methoxy groups; each R₄independently is hydrogen, an alkyl group containing not more than about4 carbon atoms, a cyanoalkyl group containing not more than about 4carbon atoms, a phenyl group or a benzyl group; R is a polymethylenegroup containing from about 4 to about 12 carbon atoms, or a grouping ofthe formula --(CH₂)_(a) --G--(CH₂)_(b) --where a and b are eachindependently 1, 2 or 3 and G is a 1,3-phenylene group, a 1,4-phenylenegroup, a methoxy-substituted-1,4-phenylene group, a 9,9-fluorylenegroup, an imino group or a methylimino group, subject to the provisothat when G is an imino group or a methylimino group, the sum of a and bis at least 4; and X and Y are each independently an o-phenylene,ethylene, trimethylene, 2-(2-pyridyl)-trimethylene,2-methyl-substituted-trimethylene or2-(N-methyl-2-2-pyridino)-trimethylene group, said solution adsorbingoxygen from said gaseous oxygen-containing feed stream; (b) desorbingoxygen from said solution to a gaseous product stream; and (c)collecting oxygen from the product stream after the oxygen has beendesorbed.
 137. The process of claim 135 wherein said desorption ofoxygen is accomplished by bringing said solution into contact with agaseous product stream with an oxygen partial pressure substantiallyless than that of said feed stream.
 138. The process of claim 136wherein said desorption of oxygen is accomplished by bringing saidsolution into contact with a gaseous product stream with an oxygenpartial pressure substantially less than that of said feed stream. 139.The process of claim 135 wherein said desorption of oxygen isaccomplished by heating said solution and bringing it into contact withsaid gaseous product stream.
 140. The process of claim 136 wherein saiddesorption of oxygen is accomplished by heating said solution andbringing it into contact with said gaseous product stream.
 141. Theprocess of claim 139 wherein the temperature of said feed stream isbetween about -41.5° C. and +40° C. and the temperature of the productstream is at least about 30° C. higher than the temperature of theproduct stream.
 142. The process of claim 140 wherein the temperature ofsaid feed stream is between about -41.5° C. and +40° C. and thetemperature of the product stream is at least about 30° C. higher thanthe temperature of the product stream.
 143. The process of claim 135wherein the metal is cobalt.
 144. The process of claim 136 wherein themetal is cobalt.
 145. The process of claim 137 wherein the oxygenpartial pressure of the product steam is at least about 110 mm. Hg. lessthan the partial pressure of the feed stream.
 146. The process of claim138 wherein the oxygen partial pressure of the product steam is at leastabout 110 mm. Hg. less than the partial pressure of the feed stream.147. The process of claim 145 wherein the oxygen partial pressure of thefeed stream is substantially atmospheric.
 148. The process of claim 146wherein the oxygen partial pressure of the feed stream is substantiallyatmospheric.
 149. The process of claim 136 wherein the rates ofabsorption of oxygen into or desorption of oxygen are increased byagitating said solution or by increasing the interfacial area betweensaid feed stream and said solution, said interfacial area beingincreased by any of the following methods:(a) bubbling said feed streamthrough said solution; (b) spraying said solution through said feedstream; or (c) contacting said solution with said feed stream in apacked column.
 150. The process of claim 136 wherein the rates ofabsorption of oxygen into or desorption of oxygen are increased byagitating said solution or by increasing the interfacial area betweensaid feed stream and said solution, said interfacial area beingincreased by any of the following methods:(a) bubbling said feed streamthrough said solution; (b) spraying said solution through said feedstream; or (c) contacting said solution with said feed stream in apacked column.
 151. The process of claim 135 conducted at a temperatureof between about -41.5° C. and +40° C.
 152. The process of claim 136conducted at a temperature of between about -41.5° C. and +40° C. 153.The process of claim 135 wherein the solvent is selected from nitriles,amines, water and mixtures thereof, andthe axial base is selected fromimidazoles and pyridines.
 154. The process of claim 136 wherein thesolvent is selected from nitriles, amines, water and mixtures thereof,andthe axial base is selected from imidazoles and pyridines.
 155. Theprocess of claim 153 wherein the solvent is dimethylformamide and theaxial base is selected from at least one of 1-methylimidazole andpyridine.
 156. The process of claim 154 wherein the solvent isdimethylformamide and the axial base is selected from at least one of1-methylimidazole and pyridine.
 157. The process of claim 155 whereinthe oxygen carrier is a salt of a cation having the formula ##STR42##wherein: R is as defined in claim 135;R₃ is methyl or benzyl; and R₄ ishydrogen or methyl; X is an ethylene or trimethylene group.
 158. Theprocess of claim 156 wherein the oxygen carrier is a salt of a cationhaving the formula ##STR43## wherein: R is as defined in claim 151;R₃ ismethyl or benzyl; and R₄ is hydrogen or methyl; X is an ethylene ortrimethylene group.
 159. A solution useful for the separation of oxygenand nitrogen from atmospheric air comprising a solvent or solventmixture, an axial base and an oxygen carrier, said solvent or solventmixture being capable of dissolving said axial base and said oxygencarrier when they are present together, said axial base being capable ofproviding a coordinating atom to the oxygen carrier, and said oxygencarrier being a metal-containing complex which is a salt of a cationhaving the structurewherein: ##STR44## M is a metal selected fromcobalt, iron, copper, nickel, manganese, ruthenium or rhodium; n⁺ is apositive oxidation state of M, n being not greater than 3; each R₁independently is hydrogen or a methyl group; each R₂ independently ishydrogen or a methyl group; each R₃ independently is hydrogen, an alkylgroup containing not more than about 17 carbon atoms, a benzyl group, aphenyl group, or a phenyl group substituted by a halogen atom or by oneor two methoxy groups; each R₄ independently is hydrogen, an alkyl groupcontaining not more than about 4 carbon atoms, a cyanoalkyl groupcontaining not more than about 4 carbon atoms, a phenyl group or abenzyl group; R is a polymethylene group containing from about 4 toabout 12 carbon atoms, or a grouping of the formula --(CH₂)_(a)--G--(CH₂)_(b) --where a and b are each independently 1, 2 or 3 and G isa 1,3-phenylene group, a 1,4-phenylene group, amethoxy-substituted-1,4-phenylene group, a 9,9-fluorylene group, animino group or a methylimino group, subject to the proviso that when Gis an imino group or a methylimino group, the sum of a and b is at least4; and X and Y are each independently an o-phenylene, ethylene,trimethylene, 2-(2-pyridyl)-trimethylene,2-methyl-substituted-trimethylene or 2-(N-methyl-2-2pyridino)-trimethylene group.
 160. The solution of claim 159 wherein thesolvent is selected from nitriles, amines, water and mixtures thereof,and the axial base is selected from imidazoles and pyridines.
 161. Thesolution of claim 160 wherein the solvent is dimethylformamide, theaxial base is selected from at least one of 1-methylimidazole andpyridine, and the oxygen carrier is a salt of a cation having theformula ##STR45## wherein: R is as defined in claim 135;R₃ is methyl orbenzyl; and R₄ is hydrogen or methyl; X is an ethylene or trimethylenegroup.
 162. A process for the separation and purification of oxygen andnitrogen comprising:(a) bring an atmospheric air feed stream intocontact with a solution containing a solvent or solvent mixture, anaxial base and an oxygen carrier when they are present together, saidaxial ase being capable of providing a coordinating atom to the oxygencarrier, and said oxygen carrier being a metal-containing complex whichis a salt of a cation having the structure ##STR46## wherein: M is ametal selected from cobalt, iron, copper, nickel, manganese, rutheniumor rhodium;n⁺ is a positive oxidation state of M, n being not greaterthan 3; each R₁ independently is hydrogen or a methyl group; each R₂independently is hydrogen or a methyl group; each R₄ independently ishydrogen, an alkyl group containing not more than about 4 carbon atoms,a cyanoalkyl group containing not more than about 4 carbon atoms, aphenyl group or a benzyl group; R₅ is a polymethylene group containingfrom 7 to about 12 carbon atoms or a m- or p-xylylene group; and each R₆independently is hydrogen or a methyl group.
 163. A process for theseparation and purification of oxygen comprising:bringing a gaseous,oxygen-containing feed stream into contact with a solution containing asolvent or solvent mixture, an axial base and an oxygen carrier, saidsolvent mixture being capable of dissolving the axial base and theoxygen carrier when they are present together, said axial base beingcapable of providing a coordinating atom to the oxygen carrier, and saidoxygen carrier being a metal-containing complex which is a salt of acation having the formula ##STR47## wherein: M is a metal selected fromcobalt, iron, copper, nickel, manganese, ruthenium or rhodium; n⁺ is apositive oxidation state of M, n being not greater than 3; each R₁independently is hydrogen or a methyl group; each R₂ independently ishydrogen or a methyl group; each R₄ independently is hydrogen, an alkylgroup containing not more than about 4 carbon atoms, a cyanoalkyl groupcontaining not more than about 4 carbon atoms, a phenyl group or abenzyl group; R₅ is a polymethylene group containing from 7 to about 12carbon atoms or a m- or p-xylylene group; and each R₆ independently ishydrogen or a methyl group.
 164. The process of claim 162 wherein saiddesorption of oxygen is accomplished by bringing said solution intocontact with a gaseous product stream with an oxygen partial pressuresubstantially less than that of said feed stream.
 165. The process ofclaim 163 wherein said desorption of oxygen is accomplished by bringingsaid solution into contact with a gaseous product stream with an oxygenpartial pressure substantially less than that of said feed stream. 166.The process of claim 162 wherein said desorption of oxygen isaccomplished by heating said solution and bringing it into contact withsaid gaseous product stream.
 167. The process of claim 162 wherein saiddesorption of oxygen is accomplished by heating said solution andbringing it into contact with said gaseous product stream.
 168. Theprocess of claim 166 wherein the temperature of said feed stream isbetween about -41.5° C. and +40° C. and the temperature of the productstream is at least about 30° C. higher than the temperature of theproduct stream.
 169. The process of claim 167 wherein the temperature ofsaid feed stream is between about -41.5° C. and +40° C. and thetemperature of the product stream is at least about 30° C. higher thanthe temperature of the product stream.
 170. The process of claim 162wherein the metal is cobalt.
 171. The process of claim 163 wherein themetal is cobalt.
 172. The process of claim 164 wherein the oxygenpartial pressure of the product steam is at least about 110 mm. Hg. lessthan the partial pressure of the feed stream.
 173. The process of claim165 wherein the oxygen partial pressure of the product steam is at leastabout 110 mm. Hg. less than the partial pressure of the feed stream.174. The process of claim 164 wherein the oxygen partial pressure of thefeed stream is substantially atmospheric.
 175. The process of claim 165wherein the oxygen partial pressure of the feed stream is substantiallyatmospheric.
 176. The process of claim 162 wherein the rates ofabsorption of oxygen into or desorption of oxygen are increased byagitating said solution or by increasing the interfacial area betweensaid feed stream and said solution, said interfacial area beingincreased by any of the following methods:(a) bubbling said feed streamthrough said solution; (b) spraying said solution through said feedstream; or (c) contacting said solution with said feed stream in apacked column.
 177. The process of claim 163 wherein the rates ofabsorption of oxygen into or desorption of oxygen are increased byagitating said solution or by increasing the interfacial area betweensaid feed stream and said solution, said interfacial area beingincreased by any of the following methods:(a) bubbling said feed streamthrough said solution; (b) spraying said solution through said feedstream; or (c) contacting said solution with said feed stream in apacked column.
 178. The process of claim 162 conducted at a temperatureof between about -41.5° C. and +40° C.
 179. The process of claim 163conducted at a temperature of between about -41.5° C. and +40° C. 180.The process of claim 162 wherein the solvent is selected from nitriles,amines, water and mixtures thereof, andthe axial base is selected fromimidazoles and pyridines.
 181. The process of claim 163 wherein thesolvent is selected from nitriles, amines, water and mixtures thereof,andthe axial base is selected from imidazoles and pyridines.
 182. Theprocess of claim 180 wherein the solvent is dimethylformamide and theaxial base is selected from at least one of 1-methylimidazole andpyridine.
 183. The process of claim 181 wherein the solvent isdimethylformamide and the axial base is selected from at least one of1-methylimidazole and pyridine.
 184. A solution useful for theseparation of oxygen and nitrogen from atmospheric air comprising asolvent or solvent mixture, an axial base and an oxygen carrier, saidsolvent or solvent mixture being capable of dissolving said axial baseand said oxygen carrier when they are present together, said axial basebeing capable of providing a coordinating atom to the oxygen carrier,and said oxygen carrier being a metal-containing complex which is a saltof a cation having the structure ##STR48## wherein: M is a metalselected from cobalt, iron, copper, nickel, manganese, ruthenium orrhodium;n⁺ is a positive oxidation state of M, n being not greater than3; each R₁ independently is hydrogen or a methyl group; each R₂independently is hydrogen or a methyl group; each R₄ independently ishydrogen, an alkyl group containing not more than about 4 carbon atoms,a cyanoalkyl group containing not more than about 4 carbon atoms, aphenyl group or a benzyl group; R₅ is a polymethylene group containingfrom 7 to about 12 carbon atoms or a m- or p-xylylene group; and each R₆independently is hydrogen or a methyl group.
 185. The solution of claim184 wherein the solvent is selected from nitriles, amines, water andmixtures thereof, and the axial base is selected from imidazoles andpyridines.
 186. A solution useful for the separation of oxygen andnitrogen from atmospheric air comprising a solvent or solvent mixture,an axial base and an oxygen carrier, said solvent or solvent mixturebeing capable of dissolvent the axial based and the oxygen carrier whenthey are present together, said axial base being capable of providing acoordinating atom to the oxygen carrier, and said oxygen carrier being amutual-containing complex having any of the structures: ##STR49##wherein M is metal selected from cobalt, iron, copper, nickel,manganese, ruthenium or rhodium; X is --O--, --S-- ##STR50## R ishydrogen alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety;and Y is halide, nitrate, thiocyanate or cyanide.
 187. A process for theseparation and purification of oxygen and nitrogen comprising:(a)bringing atmospheric air into contact with a membrane, said membraneseparating said atmospheric air into a feed stream on one side of saidmembrane and a product stream on the other side of said membrane, (b)maintaining the oxygen partial pressure on the product-stream side ofsaid membrane lower than the oxygen partial pressure on the feed-streamside of said membrane, (c) collecting oxygen from the product-streamside of said membrane, (d) said membrane comprising a membrane support,said membrane support containing a solvent or solvent mixture, an axialbase, and an oxygen carrier, said solvent or solvent mixture, axialbase, and oxygen carrier being in the liquid phase when presenttogether, said solvent or solvent mixture being capable of dissolvingthe axial base and the oxygen carrier when they are present together,said axial base being capable of providing a coordinating atom to theoxygen carrier, and said oxygen carrier being a metal-containing complexhaving either of the structures ##STR51## wherein M is a metal selectedfrom cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; n⁺is a positive oxidation state of M, n being not greater than 3: inFormula I, each R₁ is hydrogen and each R₂ is methyl, while in FormulaIII, each R₁ and R₂ independently is hydrogen or a methyl group; each R₃independently is hydrogen, alkyl or aryl; each R₄ independently ishydrogen, or an alkyl or aryl group; R is an alkylene or arylene groupor a nitrogen-containing moiety; R₅ is an alkylene or arylene group;each R₆ independently is hydrogen or an alkyl group; and X and Y areeach independently an alkylene or arylene group or a nitrogen-containingmoiety.
 188. A process for the separation and purification of oxygencomprising:(a) bringing a gaseous oxygen-containing stream into contactwith a membrane, said membrane separating said gaseous oxygen-containingstream into a feed stream on one side of said membrane and a productstream on the other side of said membrane, (b) maintaining the oxygenpartial pressure on the product-stream side of said membrane lower thanthe oxygen partial pressure on the feed-stream side of said membrane,(c) collecting oxygen from the product-stream side of said membrane, (d)said membrane comprising a membrane support, said membrane supportcontaining a solvent or solvent mixture, an axial base, and an oxygencarrier, said solvent or solvent mixture, axial base, and oxygen carrierbeing in the liquid phase when present together, said solvent or solventmixture being capable of dissolving the axial base and the oxygencarrier when they are present together, said axial base being capable ofproviding a coordinating atom to the oxygen carrier, and said oxygencarrier being a metal-containing complex having either of the structures##STR52## wherein m is a metal selected from cobalt, iron, copper,nickel, manganese, ruthenium or rhodium; n⁺ is a positive oxidationstate of M, n being not greater than 3: in Formula I, each R₁ ishydrogen and each R₂ is methyl, while in Formula III, each R₁ and R₂independently is hydrogen or a methyl group; each R₃ independently ishydrogen, alkyl or aryl; each R₄ independently is hydrogen, or an alkylor aryl group; R is an alkylene or arylene group or anitrogen-containing moiety; R₅ is an alkylene or arylene group; each R₆independently is hydrogen or an alkyl group; and X and Y are eachindependently an alkylene or arylene group or a nitrogen-containingmoiety.
 189. A process for the separation and purification of oxygen andnitrogen comprising:(a) bringing atmospheric air into contact with amembrane, said membrane separating said atmospheric air into a feedstream on one side of said membrane and a product stream on the otherside of said membrane, (b) maintaining the temperature on theproduct-stream side of said membrane higher than the temperature on thefeed-stream side of said membrane, (c) collecting oxygen from theproduct-stream side of said membrane, (d) said membrane comprising amembrane support, said membrane support containing a solvent or solventmixture, an axial base, and an oxygen carrier, said solvent or solventmixture, axial base, and oxygen carrier being in the liquid phase whenpresent together, said solvent or solvent mixture being capable ofdissolving the axial base and the oxygen carrier when they are presenttogether, said axial base being capable of providing a coordinating atomto the oxygen carrier, and said oxygen carrier being a metal-containingcomplex having either of the structures ##STR53## wherein M is a metalselected from cobalt, iron, copper, nickel, manganese, ruthenium orrhodium; n⁺ is a positive oxidation state of M, n being not greater than3: in Formula I, each R₁ is hydrogen and each R₂ is methyl, while inFormula III, each R₁ and R₂ independently is hydrogen or a methyl group;each R₃ independently is hydrogen, alkyl or aryl; each R₄ independentlyis hydrogen, or an alkyl or aryl group; R is an alkylene or arylenegroup or a nitrogen-containing moiety; R₅ is an alkylene or arylenegroup; each R₆ independently is hydrogen or an alkyl group; and X and Yare each independently an alkylene or arylene group or anitrogen-containing moiety.
 190. A process for the separation andpurification of oxygen comprising:(a) bringing a gaseousoxygen-containing stream into contact with a membrane, said membraneseparating said gaseous oxygen-containing stream into a feed stream onone side of said membrane and a product stream on the other side of saidmembrane, (b) maintaining the temperature on the product-stream side ofsaid membrane higher than the temperature on the feed-stream side ofsaid membrane, (c) collecting oxygen from the product-stream side ofsaid membrane, (d) said membrane comprising a membrane support, saidmembrane support containing a solvent or solvent mixture, an axial base,and an oxygen carrier, said solvent or solvent mixture, axial base, andoxygen carrier being in the liquid phase when present together, saidsolvent or solvent mixture being capable of dissolving the axial baseand the oxygen carrier when they are present together, said axial basebeing capable of providing a coordinating atom to the oxygen carrier,and said oxygen carrier being a metal-containing complex having eitherof the structures ##STR54## wherein M is a metal selected from cobalt,iron, copper, nickel, manganese, ruthenium or rhodium; n⁺ is a positiveoxidation state of M, n being not greater than 3: in Formula I, each R₁is hydrogen and each R₂ is methyl, while in Formula III, each R₁ and R₂independently is hydrogen or a methyl group; each R₃ independently ishydrogen, alkyl or aryl; each R₄ independently is hydrogen, or an alkylor aryl group; R is an alkylene or arylene group or anitrogen-containing moiety; R₅ is an alkylene or arylene group; each R₆independently is hydrogen or an alkyl group; and X and Y are eachindependently an alkylene or arylene group or a nitrogen-containingmoiety.
 191. The process of claim 187 or 188 wherein the oxygen partialpressure on the feed-stream side of said membrane is substantiallyatmospheric or less than atmospheric.
 192. The process of claim 187 or188 wherein the oxygen partial pressure on the feed-stream side of saidmembrane is at least about 10 mm Hg high than atmospheric.
 193. Theprocess of claim 187 or 188 conducted at a temperature of between about-50° C. and +100° C.
 194. The process of claim 189 or 190 wherein thetemperature on the feed-stream side of said membrane is between about-50° C and +95° C.
 195. The process of claim 187, 188, 189 or 190wherein the metal is cobalt.
 196. The process of claim 187 or 188wherein the solvent or solvent mixture is selected from nitriles,amines, water and mixtures thereof, andthe axial base is selected fromimidazoles and pyridines.
 197. The process of claim 187 or 188 whereinthe solvent is dimethylformamide, andthe axial base is selected from atleast one of 1-methylimidazole and pyridine.
 198. The process of claim187 or 188 wherein the oxygen carrier is ##STR55## wherein R is asdefined in claim 203;R₄ is hydrogen or methyl; R₃ is methyl or benzyl;and X is alkyl containing 2 to 3 carbon atoms.
 199. A membrane usefulfor the separation of oxygen and nitrogen from atmospheric aircomprising a membrane support, said membrane support containing asolvent or solvent mixture, axial base, and oxygen carrier, said solventor solvent mixture, axial base, and oxygen carrier being in the liquidphase when present together, said solvent or solvent mixture beingcapable of dissolving the axial base and the oxygen carrier when theyare present together, said axial base being capable of providing acoordinating atom to the oxygen carrier, and said oxygen carrier being ametal-containing complex having either of the structures ##STR56##wherein M is a metal selected from cobalt, iron, copper, nickel,manganese, ruthenium or rhodium;n⁺ is a positive oxidation state of M, nbeing not greater than 3: in Formula I, each R₁ is hydrogen and each R₂is methyl, while in Formula III, each R₁ and R₂ independently ishydrogen or a methyl group; each R₃ independently is hydrogen, alkyl oraryl; each R₄ independently is hydrogen, or an alkyl or aryl group; R isan alkylene or arylene group or a nitrogen-containing moiety; R₅ is analkylene or arylene group; each R₆ independently is hydrogen or an alkylgroup; and X and Y are each independently an alkylene or arylene groupor a nitrogen-containing moiety.
 200. The membrane of claim 199 whereinthe solvent or solvent mixture is selected from nitriles, amines, waterand mixtures thereof, andthe axial base is selected from imidazoles andpyridines.
 201. The membrane of claim 199 wherein the solvent isdimethylformamide,the axial base is selected from at least one of1-methylimidazole and pyridine, and the oxygen carrier is ##STR57##wherein R is as defined in claim 203; R₄ is hydrogen or methyl; R₃ ismethyl or benzyl; and X is alkyl containing 2 to 3 carbon atoms. 202.The membrane of claim 199 wherein the solvent or solvent mixturecontains an additive selected from the group consisting of less than orequal to 20% by weight of water or an inorganic acid or base. 203.Apparatus for the separation and purification of oxygen and nitrogencomprising:(a) membrane means, (b) means for bringing atmospheric airinto contact with said membrane means, said membrane means separatingsaid atmospheric air into a feed stream on one side of said membranemeans and a product stream on the other side of said membrane means, (c)means for maintaining the oxygen partial pressure on the product-streamside of said membrane means lower than the oxygen partial pressure onthe feed-stream side of said membrane means, (d) means for collectingoxygen from the product-stream side of said membrane means, (e) saidmembrane means comprising a membrane support, said membrane supportcontaining a solvent or solvent mixture, an axial base, and an oxygencarrier, said solvent or solvent mixture, axial base, and oxygen carrierbeing in the liquid phase when present together, said solvent or solventmixture being capable of dissolving the axial base and the oxygencarrier when they are present together, said axial base being capable ofproviding a coordinating atom to the oxygen carrier, and said oxygencarrier being a metal-containing complex having either of the structures##STR58## wherein M is a metal selected from cobalt, iron, copper,nickel, manganese, ruthenium or rhodium; n⁺ is a positive oxidationstate of M, n being not greater than 3: in Formula I, each R₁ ishydrogen and each R₂ is methyl, while in Formula III, each R₁ and R₂independently is hydrogen or a methyl group; each R₃ independently ishydrogen, alkyl or aryl; each R₄ independently is hydrogen, or an alkylor aryl group; R is an alkylene or arylene group or anitrogen-containing moiety; R₅ is an alkylene or arylene group; each R₆independently is hydrogen or an alkyl group; and X and Y are eachindependently an alkylene or arylene group or a nitrogen-containingmoiety.
 204. Apparatus for the separation and purification of oxygencomprising:(a) a membrane means, (b) means for bringing a gaseousoxygen-containing stream into contact with said membrane means, saidmembrane means separating said gaseous oxygen-containing stream into afeed stream on one side of said membrane means and a product stream onthe other side of said membrane means, (c) means for maintaining theoxygen partial pressure on the product-stream side of said membranemeans lower than the oxygen partial pressure on the feed-stream side ofsaid membrane means. (d) means for collecting oxygen from theproduct-stream side of said membrane means, (e) said membrane meanscomprising a membrane support, said membrane support containing asolvent or solvent mixture, an axial base, and an oxygen carrier, saidsolvent or solvent mixture, axial base, and oxygen carrier being in theliquid phase when present together, said solvent or solvent mixturebeing capable of dissolving the axial base and the oxygen carrier whenthey are present together, said axial base being capable of providing acoordinating atom to the oxygen carrier, and said oxygen carrier being ametal-containing complex having either of the structures ##STR59##wherein M is a metal selected from cobalt, iron, copper, nickel,manganese, ruthenium or rhodium; n⁺ is a positive oxidation state of M,n being not greater than 3: in Formula I, each R₁ is hydrogen and eachR₂ is methyl, while in Formula III, each R₁ and R₂ independently ishydrogen or a methyl group; each R₃ independently is hydrogen, alkyl oraryl; each R₄ independently is hydrogen, or an alkyl or aryl group; R isan alkylene or arylene group or a nitrogen-containing moiety; R₅ is analkylene or arylene group; each R₆ independently is hydrogen or an alkylgroup, and X and Y are each independently an alkylene or arylene groupor a nitrogen-containing moiety.
 205. Apparatus for the separation andpurification of oxygen and nitrogen comprising:(a) membrane means, (b)means for bringing atmospheric air into contact with said membranemeans, said membrane means separating said atmospheric air into a feedstream on one side of said membrane means and a product stream on theother side of said membrane means, (c) temperature maintenance means formaintaining the temperature on the product-stream side of said membranemeans higher than the temperature on the feed-stream side of saidmembrane means, (d) means for collecting oxygen from the product-streamside of said membrane means, (e) said membrane means comprising amembrane support, said membrane support containing a solvent or solventmixture, an axial base, and an oxygen carrier, said solvent or solventmixture, axial base, and oxygen carrier being in the liquid phase whenpresent together, said solvent or solvent mixture being capable ofdissolving the axial base and the oxygen carrier when they are presenttogether, said axial base being capable of providing a coordinating atomto the oxygen carrier, and said oxygen carrier being a metal-containingcomplex having either of the structures ##STR60## wherein M is a metalselected from cobalt, iron, copper, nickel, manganese, ruthenium orrhodium; n⁺ is a positive oxidation state of M, n being not greater than3: in Formula I, each R₁ is hydrogen and each R₂ is methyl, while inFormula III, each R₁ and R₂ independently is hydrogen or a methyl group;each R₃ independently is hydrogen, alkyl or aryl; each R₄ independentlyis hydrogen, or an alkyl or aryl group; R is an alkylene or arylenegroup or a nitrogen-containing moiety; R₅ is an alkylene or arylenegroup; each R₆ independently is hydrogen or an alkyl group; and X and Yare each independently an alkylene or arylene group or anitrogen-containing moiety.
 206. Apparatus for the separation andpurification of oxygen comprising:(a) membrane means, (b) means forbringing a gaseous oxygen-containing stream into contact with saidmembrane means, said membrane means separating said gaseousoxygen-containing stream into a feed stream on one side of said membranemeans and a product stream on the other side of said membrane means, (c)temperature maintenance means for maintaining the temperature on theproduct-stream side of said membrane means higher than the temperatureon the feed-stream side of said membrane means, (d) means for collectingoxygen from the product-stream side of said membrane means, (e) saidmembrane means comprising a membrane support, said membrane supportcontaining a solvent or solvent mixture, an axial base, and an oxygencarrier, said solvent or solvent mixture, axial base, and oxygen carrierbeing in the liquid phase when present together, said solvent or solventmixture being capable of dissolving the axial base and the oxygencarrier when they are present together, said axial base being capable ofproviding a coordinating atom to the oxygen carrier, and said oxygencarrier being a metal-containing complex having either of the structures##STR61## wherein M is a metal selected from cobalt, iron, copper,nickel, manganese, ruthenium or rhodium; n⁺ is a positive oxidationstate of M, n being not greater than 3: in Formula I, each R₁ ishydrogen and each R₂ is methyl, while in Formula III, each R₁ and R₂independently is hydrogen or a methyl group; each R₃ independently ishydrogen, alkyl or aryl; each R₄ independently is hydrogen, or an alkylor aryl group; R is an alkylene or arylene group or anitrogen-containing moiety; R₅ is an alkylene or arylene group; each R₆independently is hydrogen or an alkyl group; and X and Y are eachindependently an alkylene or arylene group or a nitrogen-containingmoiety.
 207. The apparatus of claim 203, 204, 205 or 206 wherein themetal is cobalt.
 208. The apparatus of claim 203, 204, 205 or 206wherein the solvent or solvent mixture is dimethylformamide,the axialbase is selected from at least one of 1-methylimidazole and pyridine,and the oxygen carrier is ##STR62## wherein R is as defined in claim203; R₄ is hydrogen or methyl; R₃ is methyl or benzyl; and X is alkylcontaining 2 to 3 carbon atoms.